KR20150023757A - Laminate - Google Patents

Abstract

It is an object of the present invention to provide a laminated body having a surface layer that is excellent in antifouling property and scratch resistance that can easily remove contamination. This embodiment is a laminate having a surface layer having a surface on which a fine concavo-convex structure is formed, wherein the surface layer has a modulus of elasticity of less than 250 MPa and a slope of the coefficient of friction of the surface layer is 0.0018 or less.

Description

Laminate {LAMINATE}

This embodiment relates to a laminate having a fine concave-convex structure and an antireflection article, an image display device, and a touch panel using the same.

The present application is based on Japanese Patent Application No. 2012-135981 and Patent Application No. 2012-135983 filed on June 15, 2012, Patent Application No. 2012-201734 filed on September 13, 2012, The present application claims priority based on Japanese Patent Application No. 2012-249312, filed on March 13, 2005, the contents of which are incorporated herein by reference.

At the interface (surface) in contact with air such as various displays, lenses, and window displays, the visibility is deteriorated due to the reflection of sunlight or illumination from the surface. As a method for reducing reflection, there has been known a method of laminating several layers of films having different refractive indices such that reflected light from the film surface and reflected light from the interface between the film and the substrate are canceled by interference. These films are usually produced by a method such as sputtering, vapor deposition, coating or the like. However, in such a method, even if the number of laminated films is increased, there is a limit to lowering the reflectivity and the wavelength dependency of the reflectance. Further, in order to reduce the number of laminated layers in order to reduce the manufacturing cost, a material having a lower refractive index has been required.

In order to lower the refractive index of the material, it is effective to introduce air into the material by some method. As a method for lowering the refractive index of the film surface, for example, a method of forming a fine uneven structure on the surface of a film is widely known. According to these methods, since the refractive index of the entire surface of the surface on which the fine concavo-convex structure is formed is determined by the volume ratio of the material forming the air and the fine concavo-convex structure, the refractive index can be largely lowered. As a result, the number of laminated layers can at least reduce the reflectance.

An antireflection film formed on a glass substrate, in which pyramidal convex portions are formed continuously on the entire film, has been proposed (see, for example, Patent Document 1). As described in Patent Document 1, the antireflection film on which the pyramidal projections (fine concavo-convex structures) are formed has a cross sectional area continuously changed when the fine concavo-convex structure is cut on the plane parallel to the film plane, The refractive index is gradually increased toward the side of the reflection surface. Further, the antireflection film shows excellent optical performance.

The antireflection film formed by such a fine concavo-convex structure has antifouling properties because it is in contact with air.

As a method for imparting antifouling property, a method of forming a coating film of polytetrafluoroethylene on the surface of a micro concavo-convex structure (see, for example, Patent Document 2) or a method of forming a fine And a method of pressing the stamper having the concavo-convex structure (see, for example, Patent Document 3). In these methods, antifouling properties are imparted because the surface energy is lowered and contamination is not emitted.

A method of coating a photocatalytic layer (such as titanium oxide) having a fine concavo-convex structure on the surface of a substrate (see, for example, Patent Document 4) or a method of forming a hydrophilic film comprising an inorganic oxide such as a silicic acid compound on the surface of a substrate by sputtering (See, for example, Patent Document 5), a method of spin-coating an inorganic microfine particle solution on the surface of soda glass and then curing by heating (see, for example, Patent Document 6). In these methods, the surface is made hydrophilic so that the adhered contamination is floated with water to make it easier to wipe off.

Patent Document 7 discloses a photocurable composition comprising a specific fluorinated surfactant and a polymerizable compound having a specific composition as a coating material for an optical disk.

Further, as disclosed in Patent Document 8, there is proposed a method of reducing the elastic modulus of the material forming the fine concavo-convex structure to thereby push out the dirt contained in the concave portion.

Japanese Patent Application Laid-Open No. 63-75702 Japanese Patent Application Laid-Open No. 2003-172808 Japanese Patent Application Laid-Open No. 2005-97371 Japanese Patent Application Laid-Open No. 2001-183506 Japanese Patent Application Laid-Open No. 2001-315247 Japanese Patent Application Laid-Open No. 11-217560 Japanese Patent Application Laid-Open No. 7-316468 Japanese Patent Application Laid-Open No. 11-76072

As described in Patent Documents 2 and 3, if the surface energy is lowered, the contamination is less likely to adhere. However, in use, the concave portion may be contaminated, and once the contamination is adhered, it may be difficult to remove the contamination.

Further, in the case where a photocatalyst is used as described in Patent Document 4, there is a case where the decomposition of the contamination is difficult to proceed with the light in the room. Further, when a photocatalyst layer is coated on the surface of a resin film or the like as a substrate, the resin film may be decomposed.

In the antifouling article having a fine concavo-convex structure obtained by the sputtering method described in Patent Documents 5 and 6, it may be difficult to adjust the distance between neighboring convex portions and the height of the convex portion, There are cases where it is not sufficiently obtained.

In addition, even when the method of blending the fluorine-based surfactant described in Patent Document 7 is applied to the fine uneven structure, the antifouling property is not sufficiently given in some cases.

The effect of the method described in Patent Document 8 is confirmed in a laminate having a fine concavo-convex structure with a pitch of 250 nm or more. However, its surface layer may be inferior in scratch resistance and, for example, There was room for improvement from the viewpoint of practicality.

It is an object of the present invention to provide a laminated body having a surface layer that is excellent in antifouling property and scratch resistance that can easily remove contamination.

(1) an aspect of the present invention is a laminate including a surface layer having a surface a fine concavo-convex structure is formed, and the elastic modulus of the surface layer of less than 250MPa, also less than the slope of the friction coefficient of the surface layer of 1.8 × 10 ^-3 , And a laminate.

(2) One form of the present invention is the laminate according to (1), wherein the slope of the friction coefficient of the surface layer is not less than -2.0 x 10 < ^{-3 &} gt ;.

(3) One form of the present invention is a laminate according to (1) or (2), wherein the slope of the surface layer friction coefficient is not less than -1.8 x 10 ^{-3 and not} more than 1.0 x 10 ^-3 .

(4) One form of the present invention is a laminate according to any one of (1) to (3), wherein the surface layer has an elastic modulus of less than 160 MPa.

(5) One form of the present invention is a laminate according to any one of (1) to (4), wherein the surface layer has a modulus of elasticity of less than 100 MPa.

(6) An embodiment of the present invention is a laminate according to any one of (1) to (5), wherein the water contact angle of the surface layer is 25 ° or less or 130 ° or more.

(7) One form of the present invention is a laminate according to any one of (1) to (6), wherein the surface layer comprises a layer comprising a cured product of the active energy ray-curable resin composition.

(8) In one embodiment of the present invention, the active energy ray-curable resin composition contains 1 to 55 parts by mass of a multifunctional (meth) acrylate (A) having three or more functional groups, a bifunctional (meth) To 95 parts by mass (provided that the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass).

(9) In one embodiment of the present invention, the content of the trifunctional or higher polyfunctional (meth) acrylate (A) is 5 to 40 parts by mass, the content of the bifunctional (meth) acrylate (B) To 80 parts by mass, and the laminate described in (8).

(10) In one embodiment of the present invention, the content of the trifunctional or higher polyfunctional (meth) acrylate (A) is 10 to 30 parts by mass, the content of the bifunctional (meth) acrylate (B) By mass to 70% by mass.

(11) In one embodiment of the present invention, the active energy ray-curable resin composition further comprises 3 to 85 parts by mass of silicon (meth) acrylate (wherein the polymerizable (A) and (B) each exclude (C)). The laminate according to (8), wherein the total amount of the components is 100 parts by mass.

(12) In an embodiment of the present invention, the active energy ray-curable resin composition further contains 7 to 70 parts by mass of silicon (meth) acrylate (wherein the polymerizable (A) and (B) each exclude (C)), and the laminate according to (9).

(13) In one embodiment of the present invention, the active energy ray-curable resin composition is a laminate according to (7), which comprises a compound (D) having an SH group.

(14) In one embodiment of the present invention, the active energy ray-curable resin composition contains 0 to 95 parts by mass of a multifunctional (meth) acrylate (E) (D) in an amount of 1 to 60 parts by mass, with the proviso that the total amount of the polymerizable components is 100 parts by mass.

(15) In an embodiment of the present invention, the surface layer is a layered body according to any one of (7) to (14), wherein the surface layer is composed of a cured product of the active energy ray curable resin composition.

(16) In one embodiment of the present invention, the surface layer is formed of a layer comprising a cured product of the active energy ray-curable resin composition and a surface as a topmost layer formed on the layer of the cured product of the active energy ray- Is a laminate according to any one of (7) to (14).

(17) An embodiment of the present invention is a laminate according to any one of (1) to (15), wherein the pitch of the fine uneven structure is 100 nm or more and 250 nm or less.

(18) An embodiment of the present invention is an antireflection article comprising the laminate according to any one of (1) to (17).

(19) An aspect of the present invention is an image display apparatus having the laminate described in any one of (1) to (17).

(20) An aspect of the present invention is a touch panel comprising the laminate according to any one of (1) to (17).

According to the present embodiment, it is possible to provide a laminate having a surface layer that is excellent in antifouling property and scratch resistance that can easily remove contamination. According to the present embodiment, it is possible to obtain a laminate having excellent antifouling properties, which can remove stains easily, preferably without using water or alcohol on the surface. Further, according to the present embodiment, it is possible to obtain a laminate having excellent scratch resistance, which does not scratch the surface layer when the contamination is wiped off with cloth or the like.

1 is a schematic cross-sectional view showing an example of the structure of the laminate according to the embodiment.
2 is a schematic cross-sectional view showing an example of the structure of the laminate according to the present embodiment.
3 is a schematic cross-sectional view showing an example of the structure of the laminate according to the present embodiment.
4 is a schematic cross-sectional view showing an example of the structure of the laminate according to the embodiment.

Hereinafter, this embodiment will be described in detail.

(Embodiment 1)

1 is a schematic cross-sectional view showing an example of the configuration of the layered product 10 according to the present embodiment. In Fig. 1, a surface layer 12 made of a cured product of an active energy ray-curable resin composition is formed on the surface of a base material 11 having transparency. In the laminate 10, a fine concavo-convex structure is formed on the surface of the surface layer 12.

In the laminate 10, it is preferable that a fine uneven structure is formed on the entire surface of the surface layer, but a fine uneven structure may be formed on a part of the surface of the surface layer. When the layered product 10 has a film shape, fine concavo-convex structures may be formed on both sides of the layered product 10.

In the laminate of the present embodiment, the modulus of elasticity of the fine uneven structure region, that is, the modulus of elasticity of the surface layer is less than 250 MPa. The elastic modulus of the surface layer is preferably less than 160 MPa, more preferably 50 MPa or more and 100 MPa or less. When the elastic modulus of the surface layer is less than 250 MPa, the fine concavo-convex structure is so soft that contaminants entering the recesses can be easily pushed out. If the elastic modulus of the surface layer is less than 160 MPa, the fine concavo-convex structure is softer, so that contamination in the concave portion can be more easily pushed out. When the elastic modulus of the surface layer is 50 MPa or more, since the fine uneven structure has sufficient hardness, it is possible to effectively prevent the unevenness of the projection. When the elastic modulus of the surface layer is 100 MPa or less, the fine concavo-convex structure is sufficiently smooth, so that the fine concavo-convex structure can be freely deformed, and the contamination in the concavity can be more easily removed.

In the laminate of the present embodiment, the slope of the friction coefficient of the fine uneven structure region, that is, the slope of the friction coefficient of the surface layer is 1.8 x 10 < ^-3 > The slope of the friction coefficient of the surface layer is preferably -2.0 占^10-3 or more, more preferably -1.8 占^10-3 or more and 1.0 占^10-3 or less. When the slope of the friction coefficient of the surface layer is 0.0018 or less, the surface layer is not destroyed because the increase of the friction coefficient is small when the surface layer is rubbed with cloth or the like. When the slope of the friction coefficient of the surface layer is not less than -1.8 x 10 < ^{-3 &} gt ;, the convex portions of the fine concave-convex structure do not coalesce when the surface layer is rubbed with cloth or the like, and the antireflection performance equivalent to that before the scratching can be maintained even after the scratching. When the slope of the friction coefficient of the surface layer is 1.0 x 10 < ^-3 > or less, the surface layer is not scratched because the increase in friction coefficient is smaller when the surface layer is rubbed with cloth or the like.

The water contact angle of the fine concavo-convex structure region, that is, the water contact angle of the surface layer is not particularly limited, but is preferably 25 ° or less, or 130 ° or more, more preferably 15 ° or less or 135 ° or more. When the water contact angle of the surface layer is 25 DEG or less, the surface is hydrophilic, so that the contamination can be easily wiped off. When the water contact angle of the surface layer is 130 degrees or more, the surface energy of the surface layer is small, so that the contamination can be easily wiped off. When the water contact angle of the surface layer is 15 or less, the hydrophilicity of the surface is high, so that the contamination can be more easily wiped off. When the water contact angle of the surface layer is 135 deg. Or more, the surface energy of the surface layer is sufficiently small, so that adhesion of the contamination can be suppressed. The lower limit of the water contact angle of the surface layer is not particularly limited, but the water contact angle of the surface layer is preferably 5 deg. Or more, more preferably 7 deg. Or more. The upper limit of the water contact angle of the surface layer is not particularly limited, but the water contact angle of the surface layer is preferably 150 ° or less, and more preferably 145 ° or less.

In the laminate of the present embodiment, the surface layer may be composed of a cured product of the active energy ray-curable resin composition. Further, as described later, the surface layer may be composed of a surface treatment layer as the outermost layer formed on the layer comprising the cured product of the active energy ray-curable resin composition and the layer comprising the cured product of the active energy ray- have.

The active energy ray-curable resin composition preferably contains 1 to 55 parts by mass of a trifunctional or higher polyfunctional (meth) acrylate (A) and 10 to 95 parts by mass of a bifunctional (meth) acrylate (B) And the total amount of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass).

The active energy ray-curable resin composition preferably contains 3 to 85 parts by mass of silicon (meth) acrylate (C). That is, for example, the active energy ray-curable resin composition is obtained by mixing 1 to 55 parts by mass of a trifunctional or higher polyfunctional (meth) acrylate (A), 10 to 95 parts by mass of a bifunctional (meth) acrylate (B) It is preferable that 3 to 85 parts by mass of the silicone (meth) acrylate (C) (provided that the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass). On the other hand, the silicone (meth) acrylate (C) is excluded from the trifunctional or higher polyfunctional (meth) acrylate (A) and the bifunctional (meth) acrylate (B).

Here, the polyfunctional (meth) acrylate having three or more functional groups means at least three groups selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) ≪ / RTI > The bifunctional (meth) acrylate refers to a compound having two groups selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) in the molecule it means.

The multifunctional (meth) acrylate (A) having three or more functional groups is preferably four or more functional groups, and more preferably five or more functional groups. Examples of the multifunctional (meth) acrylate (A) having three or more functional groups include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra Condensation reaction product of dipentaerythritol hydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4, urethane acrylates , Polyether acrylates, modified epoxy acrylates, and polyester acrylates. Examples of the urethane acrylates include "EBECRYL220", "EBECRYL1290", "EBECRYL1290K", "EBECRYL5129", "EBECRYL8210", "EBECRYL8301" and "KRM8200" manufactured by Daicel-Cytec. Examples of the polyether acrylates include EBECRYL81 from Daicel-Cytec. As the modified epoxy acrylates, "EBECRYL3416" manufactured by Daicel-Cytec Co., Ltd. may be mentioned. EBECRYL850 "," EBECRYL810 "," EBECRYL811 "," EBECRYL812 "," EBECRYL1830 "," EBECRYL845 "," EBECRYL846 "and" EBECRYL846 "manufactured by Daicel-Cytec Co., &Quot; EBECRYL1870 ". Examples of the multifunctional (meth) acrylate (A) having three or more functional groups include monomers obtained by adding ethylene oxide or propylene oxide to the above monomers. These polyfunctional (meth) acrylates (A) may be used singly or in combination of two or more.

When the total amount of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass, the multifunctional (meth) acrylate (A) having three or more functionalities is preferably 1 to 55 parts by mass, more preferably 5 to 40 parts by mass And more preferably 10 to 30 parts by mass. By setting the content of the trifunctional or higher polyfunctional (meth) acrylate (A) to 1 part by mass or more, a modulus of elasticity capable of transferring the micro concavo-convex structure to the surface layer can be imparted. Further, by setting the content of the trifunctional or higher polyfunctional (meth) acrylate (A) to 55 parts by mass or less, an increase in the modulus of elasticity of the surface layer can be suppressed. As a result, contamination can be easily pushed out from the concave portion, and sufficient antifouling properties can be imparted to the laminate. When the amount is 5 parts by mass or more, a good modulus of elasticity can be imparted to the surface layer, and the projections of the convex portions in the fine concavo-convex structure can be suppressed. When the content is 40 parts by mass or less, the decrease in the mobility of the convex portion is suppressed, and the antifouling property capable of easily removing the contamination can be effectively exhibited without using water or alcohol. On the other hand, in the present specification, the projecting unity of the projections or projections means that the projections or projections adjacent to each other are formed into one.

Examples of the bifunctional (meth) acrylate (B) include bifunctional acrylates having polyethylene glycol, bifunctional acrylates having polypropylene glycol and polyalkylene glycols such as bifunctional acrylates having polybutylene glycol ≪ / RTI > is preferred. Specific examples of the bifunctional acrylates having polyethylene glycol include Aronix M-240, Aronix M-260 (manufactured by DOA Corporation), NK ester AT-20E and NK ester ATM-35E (manufactured by Shin Nakamura Chemical Co., . Specific examples of bifunctional acrylates having polypropylene glycol include APG-400 and APG-700 (manufactured by Shin Nakamura Chemical Co., Ltd.). Specific examples of bifunctional acrylates having polybutylene glycol include A-PTMG-650 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. By using a bifunctional acrylate having a polyalkylene glycol as the bifunctional (meth) acrylate (B), the elastic modulus of the surface layer is suppressed and the stain is easily pushed out from the concave portion, thereby effectively exhibiting stain resistance. Among the bifunctional acrylates having a polyalkylene glycol, polyethylene glycol diacrylate is suitably used in that a more excellent antifouling property is obtained. By using polyethylene glycol diacrylate as the bifunctional (meth) acrylate (B), the molecular mobility of the resin in the surface layer is improved, so that contamination in the recess can be more easily pushed out, and good antifouling properties are exhibited.

The total number of the average repeating units of the polyethylene glycol chain present in one molecule of the polyethylene glycol diacrylate is preferably 6 to 40, more preferably 9 to 30, and even more preferably 12 to 20. When the average repeating unit of the polyethylene glycol chain is 6 or more, the mobility of the molecule is maintained and good antifouling property is expressed. When the average repeating unit of the polyethylene glycol chain is 40 or less, compatibility with the trifunctional or higher polyfunctional (meth) acrylate (A) is improved. Among the bifunctional acrylates having polyalkylene glycol, polypropylene glycol diacrylate and polybutylene glycol diacrylate are also suitably used from the viewpoint of compatibility. (Meth) acrylate such as silicone di (meth) acrylate having a low hydrophilicity can be obtained by using polypropylene glycol diacrylate or polybutylene glycol diacrylate as the bifunctional (meth) acrylate (B) ) Is improved, and a transparent active energy ray-curable resin composition can be obtained. These bifunctional (meth) acrylates (B) may be used singly or in combination of two or more. Also, polyethylene glycol and polypropylene glycol diacrylate and / or polybutylene glycol diacrylate are preferably used in combination in view of compatibility between antifouling property and compatibility.

The bifunctional (meth) acrylate (B) is preferably 10 to 95 parts by mass, more preferably 20 to 80 parts by mass, more preferably 20 to 80 parts by mass when the sum of the polymerizable components in the active energy ray- , And more preferably 30 to 70 parts by mass. When the content of the bifunctional (meth) acrylate (B) is 10 parts by mass or more, an increase in the modulus of elasticity of the surface layer is suppressed, and the stain is easily pushed out from the concave portion. By setting the content of the bifunctional (meth) acrylate (B) to 95 parts by mass or less, it is possible to maintain the modulus of elasticity such that the fine concavo-convex structure can be transferred to the surface layer. When the content is 20 parts by mass or more, mobility can be imparted to the convex portion, and antifouling property is effectively exhibited. When the amount is 80 parts by mass or less, deterioration of the modulus of elasticity is suppressed and projections of the convex portions can be suppressed.

(CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ )) at the side chain and / or the end of the compound having an organosiloxane structure, and the silicon (meth) acrylate (C) CO-) as long as it is a compound having at least one group selected from the group consisting of The silicone (meth) acrylate (C) is preferably selected from the viewpoint of compatibility of the trifunctional or higher polyfunctional (meth) acrylate (A) with the bifunctional (meth) acrylate (C) ) As the acrylate (C), it is preferable to use a compound having a compatible segment contributing to compatibility with (A) and (B). Examples of the compatible segment include a polyalkylene oxide structure, a polyester structure, and a polyamide structure. These compatibilizing segments may be contained singly in the silicone (meth) acrylate (C), or may contain two or more species. Further, the silicone (meth) acrylate (C) may be diluted in view of handleability. As the diluent, it is preferable that the diluent has reactivity in terms of bleeding out from the cured product. (Meth) acrylate (C) by mixing a multifunctional (meth) acrylate (A) or a bifunctional (meth) acrylate (B) C can be improved.

Specific examples of such silicone (meth) acrylate (C) include Sirea plain series manufactured by Jitsu Co., Ltd., silicone diacrylate " X-22-164 ", Shin- 160K ", BYK-UV3500 " BYK-UV3570 " manufactured by Big Chemie Japan, and TEGO Rad series manufactured by Ebonic Degussa Japan. These silicone (meth) acrylates (C) may be used singly or in combination of two or more.

The amount of the silicone (meth) acrylate (C) is preferably from 3 to 85 parts by mass, more preferably from 7 to 70 parts by mass, more preferably from 20 to 70 parts by mass, By mass to 70 parts by mass. When the content of the silicone (meth) acrylate (C) is 3 parts by mass or more, the water contact angle of the surface layer having the fine uneven structure tends to become 130 degrees or more, and the antifouling property is imparted to the laminate. Further, by setting the content of the silicone (meth) acrylate (C) to 85 parts by mass or less, a modulus of elasticity capable of transferring the fine concavo-convex structure to the surface layer can be imparted. When the amount is 7 parts by mass or more, the water contact angle of the surface layer is liable to be 135 deg. Or more, and the antifouling property of the laminate is improved. When the amount is 70 parts by mass or less, the viscosity of the active energy ray-curable resin composition is suppressed and the handling property is improved. When the amount is 20 parts by mass or more, compatibility with components (A) and (B) in the active energy ray curable resin composition is improved, and the water repellency of the surface layer and the flexibility of the projections are improved, Excellent antifouling property is expressed.

The active energy ray curable resin composition may further contain a monofunctional monomer. The monofunctional monomer is preferably selected in consideration of the compatibility with the trifunctional or higher polyfunctional (meth) acrylate (A) and the bifunctional (meth) acrylate (B), and from this viewpoint, Monomolecular (meth) acrylates having a polyethylene glycol chain in the group, mono-functional (meth) acrylates having a hydroxyl group in an ester group such as a hydroxyalkyl (meth) acrylate, mono-functional acrylamides, Cationic monomers such as propyl trimethylammonium methylsulfate and methacryloyloxyethyl trimethylammonium methylsulfate, and the like, can be preferably exemplified. Specific examples of monofunctional monomers include monomolecular (meth) acrylates such as "M-20G", "M-90G" and "M-230G" (manufactured by Shin Nakamura Chemical Co., Ltd.).

In addition, a viscosity adjuster such as acryloylmorpholine or vinylpyrrolidone or an adhesion improver such as acryloyl isocyanate which improves the adhesion to a transparent substrate may be added to the active energy ray curable resin composition .

The content of the mono-functional monomer in the active energy ray-curable resin composition is preferably from 0.1 to 20 parts by mass, more preferably from 5 to 15 parts by mass, based on 100 parts by mass of the total of the polymerizable components in the active energy ray- More preferable. By including the monofunctional monomer, the adhesion between the substrate and the surface layer (active energy ray curable resin) is improved. (Meth) acrylate (A) and the bifunctional (meth) acrylate (B) can be adjusted by adjusting the content of the monofunctional monomer to 20 parts by mass or less to sufficiently exhibit the antifouling property . The monofunctional monomers may be used singly or in combination of two or more.

Further, a polymer (oligomer) having a low degree of polymerization obtained by polymerizing one or more monofunctional monomers may be added to the active energy ray curable resin composition. Specific examples of the polymer having such a low polymerization degree include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group (for example, "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd.), methacrylamide propyl tri 40/60 copolymer oligomer of methylammonium methylsulfate (e.g., " MG polymer ", manufactured by MRC Unitech Co., Ltd.).

The active energy ray-curable resin composition may contain fine particles such as an antistatic agent, a releasing agent, an ultraviolet absorber, and colloidal silica, in addition to the above-mentioned various monomers and polymers having a low degree of polymerization.

The active energy ray curable resin composition may contain a release agent. When the active energy ray-curable resin composition contains a releasing agent, good releasability can be maintained when the laminate is continuously produced. Examples of the release agent include (poly) oxyalkylene alkyl phosphoric acid compounds. Particularly, in the case of using an anodized alumina mold, the (poly) oxyalkylene alkyl phosphate compound and alumina interact with each other, so that the mold release agent is likely to be adsorbed on the surface of the mold.

JP-506H "(trade name) manufactured by JOHOKU CHEMICAL INDUSTRIAL CO., LTD.," MoldWiz INT-1856 "(trade name) manufactured by Axel Corporation, a product of Nikko Chemicals Co., TDP-8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP- DDP-2 "," TLP-4 "," TCP-5 ", and" DLP-10 "(trade names).

The release agents contained in the active energy ray-curable resin composition may be used alone or in combination of two or more.

The content of the releasing agent contained in the active energy ray-curable resin composition is preferably 0.01 to 2.0 parts by mass, more preferably 0.05 to 0.2 parts by mass based on 100 parts by mass of the polymerizable component. When the content of the releasing agent is 0.01 parts by mass or more, the releasability from the mold of the article having the fine uneven structure on the surface is good. On the other hand, when the ratio of the releasing agent is 2.0 parts by mass or less, the adhesion between the cured product of the active energy ray-curable resin composition and the base material is good, and the hardness of the cured product is adequate, whereby the fine uneven structure can be sufficiently retained.

The fine concavo-convex structure preferably has a distance w1 (pitch) between adjacent convex portions of the fine concavo-convex structure of not more than the wavelength of visible light, more preferably 100 nm or more and 300 nm or less, still more preferably 150 nm or more and 250 nm or less, And more preferably not more than 230 nm. By setting the thickness to 100 nm or more, it is possible to effectively prevent the projection-to-projection between the convex portions. By setting the thickness to 300 nm or less, the scattering of visible light is effectively suppressed, and the excellent antireflection property is easily given since the wavelength is sufficiently smaller than the wavelength of visible light.

On the other hand, in the present embodiment, "wavelength of visible light" means a wavelength of 400 nm.

The height d1 of the convex portion 13 is preferably 100 nm or more, more preferably 150 nm or more. By setting the height d1 to 100 nm or more, an increase in the minimum reflectance and an increase in the reflectance at a specific wavelength can be prevented, and good anti-reflection properties can be easily given.

The aspect ratio (the height of the convex portion 13 / the interval between adjacent convex portions) is preferably 0.5 to 5.0, more preferably 0.6 to 2.0, still more preferably 0.8 to 1.2. When the aspect ratio is 0.5 or more, it is possible to suppress the increase of the minimum reflectance and the increase of the reflectance at a specific wavelength, and thus the good antireflection property is exhibited. When the aspect ratio is 5 or less, the convex portions of the fine concave-convex structure are less likely to be broken when the surface layer is contacted, so that excellent scratch resistance and antireflection properties are exhibited.

In the present embodiment, the "height of the convex portion" means a distance from the front end 13a of the convex portion 13 to the bottom portion 14a of the adjacent concave portion 14 in the vertical direction . The shape of the convex portion 13 of the concave-convex structure is not particularly limited. However, in order to obtain an antireflection function in which the refractive index is continuously increased and the low reflectance and the low wavelength dependency are both achieved, It is preferable that the structure has such a structure that the occupancy of the cross sectional area when cut at a plane parallel to the film surface such as the shape of a bell or the like as shown in Fig. 2 is continuously increased toward the substrate side. Further, the finer convex portions may be a plurality of convexly concaved portions to form the fine convex-concave structure.

The method of forming the fine concavo-convex structure on the surface of the laminate is not particularly limited, and for example, a method of injection molding or press molding using a stamper having a micro concavo-convex structure is exemplified. As a method of forming the micro concavo-convex structure, for example, an active energy ray-curable resin composition is filled between a stamper formed with a micro concavo-convex structure and a transparent substrate, and the active energy ray curable resin composition is cured by active energy ray irradiation, A method of transferring a shape and then releasing it may be mentioned. As a method of forming the micro concavo-convex structure, there is a method of filling the active energy ray-curable resin composition between the stamper on which the micro concavo-convex structure is formed and the transparent substrate, transferring the convexo-concave shape of the stamper to the active energy ray- And thereafter irradiating an active energy ray to cure the active energy ray-curable resin composition. Among them, in view of the transferability of the concavo-convex structure and the degree of freedom of the surface composition, the active energy ray-curable resin composition is filled between the stamper on which the concave-convex structure is formed and the transparent substrate and the active energy ray- A method of releasing the convexo-concave shape of the stamper after curing and releasing it is preferably used.

The substrate is not particularly limited, but is preferably a transparent substrate. The transparent substrate is not particularly limited as long as it transmits light. Examples of the material of the transparent substrate include methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, There may be mentioned polyester, polyamide, polyimide, polyethersulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polyurethane, glass, quartz and the like. The transparent substrate may be formed by any of injection molding, extrusion molding, and casting.

The shape of the transparent substrate is not particularly limited and may be appropriately selected depending on the application. For example, when the use is an antireflection film, it is preferably a sheet or film. In addition, for the purpose of improving adhesion to the active energy ray-curable resin composition, antistatic property, scratch resistance, weather resistance, etc., the surface of the transparent substrate may be subjected to various coatings or corona discharge treatment, for example.

The method of manufacturing the stamper having the micro concavo-convex structure is not particularly limited, and examples thereof include an electron beam lithography method and a laser light interference method. For example, after a suitable photoresist film is coated on a suitable support substrate, exposure is performed using light such as ultraviolet laser, electron beam, or X-ray, and then development is performed to form a mold having a micro concavo-convex structure. This mold can be used as a stamper as it is. It is also possible to selectively etch the support substrate through the photoresist layer by dry etching and then remove the photoresist layer to form a micro concavo-convex structure directly on the support substrate itself.

Anodic oxidized porous alumina may also be used as a stamper. For example, as disclosed in Japanese Patent Application Laid-Open No. 2005-156695, an alumina nanohole array obtained by anodic oxidation of aluminum at a predetermined voltage in an electrolyte such as oxalic acid, sulfuric acid, or phosphoric acid is used as a stamper . According to this method, pores having extremely high regularity can be formed in a self-organizing manner by subjecting high-purity aluminum to anodic oxidation at a constant voltage for a long period of time, removing the oxide film once, and anodizing it again. It is also possible to form a micro concavo-convex structure having a convex shape as well as a substantially conical shape by combining the anodic oxidation treatment and the pore diameter enlarging treatment at the time of anodizing again. Further, a replica type may be produced from a circular prototype having a micro concavo-convex structure by electrophoresis or the like, and this may be used as a stamper.

The shape of the stamper produced in this manner is not particularly limited, but may be a flat plate shape or a roll shape, but a roll shape is preferable from the viewpoint of being able to continuously transfer the fine uneven structure to the active energy ray curable resin composition.

The active energy ray curable resin composition in the present embodiment may suitably contain a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer, It hardens. In addition, the active energy ray-curable resin composition may include a non-reactive polymer.

Specific examples of the active energy ray used for curing the active energy ray-curable resin composition include visible light, ultraviolet light, electron beam, plasma, and infrared light.

The light irradiation of the active energy ray is performed, for example, by using a high-pressure mercury lamp. Accumulated irradiation amount of energy, which is an active energy ray-curing of the curable resin composition proceeds amount of energy but is not particularly limited, for example 100~5000mJ / cm ² are preferred, 200~4000mJ / cm ² are more preferred, and 400 To 3200 mJ / cm < ² > is more preferable. Since the amount of irradiation of the accumulated energy of the active energy ray may influence the degree of curing of the active energy ray curable resin composition, it is preferable to appropriately select and irradiate light.

The polymerization initiator (photopolymerization initiator) used in the curing (photo-curing) of the active energy ray-curable resin composition is not particularly limited, and examples thereof include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl- Acetophenones such as morpholinophenyl) butanoic acid; Benzoin methyl ether, benzoin toluene sulfonic acid ester, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Benzophenones such as benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone, and p-chlorobenzophenone; Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Ketalization; Anthraquinones; Thioanthones; Azo compounds; peroxide; 2,3-dialkylated ionic compounds; Disulfide compounds; Fluoroamine compounds; Aromatic sulfonates and the like. These photopolymerization initiators may be used singly or in combination of two or more.

Further, the active energy ray-curable resin composition may be cured by using a combination of photo-curing and thermal curing. The thermopolymerization initiator to be added when thermosetting is used in combination is not particularly limited, and examples thereof include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'- Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile) 1-azobis (cyclohexane-1-carbonitrile), 1 - [(1 -cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy- Azo compounds such as methyl valeronitrile and dimethyl-2,2'-azobis (2-methylpropionate); Benzoyl peroxide, t-hexyl peroxyneodecanoate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxy pivalate, t-butylperoxy pivalate, 3,5,5-trimethyl hexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxyoctanoate, Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1'-bis (t-butylperoxy) (t-butylperoxy) cyclohexane, t-butylperoxybenzoate, and peroxides such as dicumylperoxide. These thermal polymerization initiators may be used alone or in combination of two or more.

The laminate according to the present embodiment can be used in various applications such as an antireflection film (including an antireflection film) and an antireflection film, an image display device, a touch panel, an optical waveguide, a relief hologram, a solar cell, A device, an optical article such as a member for improving the light extraction rate of organic electroluminescence, a cell culture sheet, and the like. The laminate of the present embodiment is particularly suitable for use as an antireflection film such as an antireflection film (including an antireflection film) and an antireflection film.

Since the laminate of the present embodiment is a laminate having a surface layer that is excellent in antifouling property and scratch resistance that can easily remove contamination, the laminate of the present embodiment is used as an antireflective article, an image display device, If it is provided on the outermost surface, contamination of sebum or the like adhered at the time of use is hardly caused, and it is easy to drop, and a good antireflection performance can be exhibited. In addition, since contamination can be easily removed without using water or alcohol on the surface, an article excellent in practical use can be obtained.

When the antireflective article is in the form of a film, it is attached to the surface of an object such as a liquid crystal display, a plasma display panel, an electroluminescence display, an image display device such as a cathode-ray tube display, a lens, .

When the antireflective article has a three-dimensional shape, a laminate may be prepared in advance using a transparent substrate having a shape corresponding to the intended use, and the laminate may be used as a member constituting the surface of the object.

When the object is an image display device, the antireflective article may be attached to the front plate instead of the surface thereof, or the front plate itself may be constituted by the laminate of the present embodiment.

(Embodiment 2)

As described above, the surface layer may be composed of a cured product of the active energy ray-curable resin composition, and in the laminate of the present embodiment, the active energy ray curable resin composition preferably contains a compound (D) having an SH group Do. The term SH refers to a syrup, a water yellow, a mercapto or a sulfhydryl group. By incorporating a compound having an SH group into the active energy ray-curable resin composition, a chemical bond between a sulfur atom and a sulfur atom or a carbon atom is obtained. In this case, since the elastic modulus can be lowered while maintaining the crosslinking density of the cured product, flexibility can be imparted to the protrusions while maintaining the shape of the protrusions, and contamination remaining in the recesses can be removed, .

In the laminate of the present embodiment, the active energy ray-curable resin composition preferably contains 0 to 95 parts by mass of a bifunctional or higher polyfunctional (meth) acrylate (E), 0 to 95 parts by mass of the above-mentioned silicone (meth) To 75 parts by mass and the SH group-containing compound (D) in an amount of 1 to 60 parts by mass (provided that the total amount of the polymerizable components is 100 parts by mass). On the other hand, the silicone (meth) acrylate (C) is excluded from the multifunctional (meth) acrylate (E) of two or more functions.

Here, the polyfunctional (meth) acrylate (E) having two or more functional groups means a group selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) Means at least two or more compounds.

Examples of the polyfunctional (meth) acrylate (E) having two or more functional groups include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxy (meth) acrylate, (Meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2- ) Propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) (Meth) acrylate, ethylene oxide adducts of bisphenol A, di (meth) acrylate, bis (3-hydroxyethyl) , Bifunctional monomers such as propylene oxide adduct di (meth) acrylate of bisphenol A, hydroxypivalic neopentyl glycol di (meth) acrylate, divinylbenzene and methylene bisacrylamide, pentaerythritol tri ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide Modified triacrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Acrylate, and tetramethylolmethane tetra (meth) acrylate, bifunctional or higher urethane acrylates, and bifunctional or higher polyester acrylates. These may be used alone or in combination of two or more.

The multifunctional (meth) acrylate (E) having two or more functionalities is preferably 0 to 95 parts by mass, more preferably 25 to 90 parts by mass when the sum of the polymerizable components in the active energy ray curable resin composition is 100 parts by mass And particularly preferably 40 to 90 parts by mass. When the content of the multifunctional (meth) acrylate (E) is more than 0 parts by mass and not more than 95 parts by mass, the excessive decrease of the modulus of elasticity can be suppressed and the shape of the protrusions can be maintained. In addition, by adding a multifunctional (meth) acrylate (E) having two or more functional groups in the composition, that is, when its content is more than 0 part by mass, the modulus of elasticity is easily suppressed and the shape of the projections can be easily maintained. When the content of the multifunctional (meth) acrylate (E) is more than 40 parts by mass, the decrease of the modulus of elasticity can be suppressed and the unevenness of the projections can be prevented more effectively. When the content of the multifunctional (meth) acrylate (E) is 95 parts by mass or less, the modulus of elasticity is lowered and the contamination can be more effectively removed. When the content is 90 parts by mass or less, the modulus of elasticity is sufficiently lowered, so that contamination of the concave portion can be more effectively removed. As a result, contamination can be easily pushed out from the concave portion, and sufficient antifouling properties can be imparted to the laminate.

In the present embodiment, when the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass, the amount of the silicone (meth) acrylate (C) is preferably 0 to 75 parts by mass, more preferably 5 to 70 parts by mass Is more preferable. When the content of the silicone (meth) acrylate (C) is 0 parts by mass or more and 75 parts by mass or less, water repellency is imparted and the antifouling property is further improved. In addition, when silicone (meth) acrylate (C) is added to the composition, that is, when its content is more than 0 part by mass, water repellency is more effectively imparted and antifouling property is improved. When the content of the silicone (meth) acrylate (C) is 5 parts by mass or more, the surface energy of the surface layer is lowered, and the contact angle with water is 130 ° or more. When the content of the silicone (meth) acrylate (C) is 75 parts by mass or less, transparency is improved because compatibility with other components is improved. When the content of the silicone (meth) acrylate (C) is 70 parts by mass or less, the viscosity of the active energy ray-curable resin composition is suppressed and the handling property is improved.

The compound (D) containing an SH group is not particularly limited as long as it is a compound containing an SH group, but it is preferably a compound containing two or more SH groups in order to increase the cross-linking density of the surface layer and maintain the strength. From the viewpoint of storage stability of the pre-curable resin composition, it is more preferable that the SH group is a secondary thiol.

Examples of the compound having two or more SH groups include 1,2-ethane dithiol, 1,2-propane dithiol, 1,3-propane dithiol, 1,4- 1,6-hexanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonenethythiol, 1,12-dodecane dithiol, 2,2-dimethyl-1,3-propane dithiol, 3-methyl-1,5-pentane dithiol, Cyclohexanedicarboxylic acid, 1,2,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylenebis (2,2,1] hepta- Dithiol compounds such as glycol bis (2-mercaptoacetate) and ethylene glycol bis (3-mercaptopropionate); 1,1,1-tris (mercaptomethyl) ethane, 2-ethyl-2-mercaptomethyl-1,3-propane dithiol, 1,2,3- Triisocyanate compounds such as pheny tris (2-mercaptoacetate), trimethylol propane tris (3-mercaptopropionate), and tris ((mercaptopropionyloxy) -ethyl) isocyanurate; Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanate), dipentaerythritol hexa-3- And thiol compounds having 4 or more SH groups such as mercaptopropionate.

Examples of the compound having a secondary thiol include a car lens MT PE1, a car lens MT NR1, and a car lens MT BD1 (trade name, manufactured by Showa Denko K.K.).

Such SH group-containing compound (D) can be suitably selected from the group consisting of "CALENS MT PE1", "CALENS MT BD1" and "CALENS MT NR1" (all trade names) manufactured by Showa Denko have.

When the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass, the compound (D) containing the SH group is preferably 1 to 60 parts by mass, more preferably 1 to 15 parts by mass. When the content of the SH group-containing compound (D) is 1 part by mass or more, the elastic modulus of the surface layer can be lowered while maintaining the crosslinking density, so that contamination can be easily pushed out from the recessed portion. As a result, And the restoring force of the shape of the convex portion can be maintained. When the content of the SH group-containing compound (D) is 60 parts by mass or less, the storage stability of the active energy ray curable resin composition can be maintained. When the content of the SH group-containing compound (D) is 15 parts by mass or less, the decrease of the elastic modulus of the surface layer can be suppressed more effectively, and the unevenness of the convex portions can be prevented.

The active energy ray curable resin composition may further contain a monofunctional monomer. The monofunctional monomer is preferably selected in consideration of the compatibility with the multifunctional (meth) acrylate (E) and the silicone (meth) acrylate (C) of two or more functional groups. Examples thereof include monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group, monofunctional (meth) acrylates having a hydroxyl group in an ester group such as a hydroxyalkyl (meth) acrylate, monofunctional acrylamides, Cationic monomers such as methacrylamide propyl trimethylammonium methylsulfate or methacryloyloxyethyl trimethylammonium methylsulfate, and the like are preferably exemplified. Specific examples of mono-functional monomers include monomolecular (meth) acrylates such as "M-20G", "M-90G", and "M-230G" (all trade names available from Shin-Nakamura Chemical Co., Ltd.). In addition, from the viewpoint of improving the antifouling property, alkyl mono (meth) acrylate, silicone (meth) acrylate and alkyl fluoro (meth) acrylate are suitably used. Specific examples of such mono-functional monomers include Nemic analogue blends such as "Blemmer LA", "Blemmer CA", "Blemmer SA" (all trade names), "X-24-8201" "X-22-174DX" (all trade names), "C10GACRY" (trade name) manufactured by Exflor Research.

(Embodiment 3)

The surface layer may be composed of a surface treatment layer as the outermost layer formed on the layer comprising the cured product of the above-mentioned active energy ray-curable resin composition and the layer comprising the cured product of the active energy ray-curable resin composition.

3 is a schematic cross-sectional view showing an example of the configuration of the layered body 110 according to the present embodiment. 3, a layer (hereinafter also referred to as a cured layer) 112 made of a cured product of an active energy ray-curable resin composition is formed on a substrate 111 having transparency, and the cured layer 112, A surface treatment layer 113 is formed as an outermost layer. In the laminate 110, the cured layer 112 has a fine uneven structure on its surface side, and the surface treated layer 113 is formed along the fine uneven structure. The surface layer 104 is composed of a cured layer 112 and a surface treatment layer 113. The shape of the micro concavo-convex structure is not limited to the shape shown in Fig. 3, and may be a shape as shown in Fig. 4 or another shape.

In the laminate of the present embodiment, the water contact angle of the fine concave-convex structure region, that is, the water contact angle of the surface treatment layer is preferably 130 ° or more, more preferably 135 ° or more. When the water contact angle of the surface treatment layer is 130 DEG or more, the surface energy is sufficiently small, so that the contamination can be easily wiped off. When the water contact angle of the surface treatment layer is 135 占 or more, adhesion of the contamination can be suppressed because the surface energy is sufficiently small. The upper limit of the water contact angle of the surface treatment layer is not particularly limited, but is preferably 150 占 or less, more preferably 145 占 or less. As the material of the surface treatment layer exhibiting such water repellency, a compound having an alkyl group, a polydimethylsiloxane structure or an alkyl fluoride group is suitably used. The material of the surface treatment layer is preferably a compound having a reactive group such as silane, alkoxysilane, silane, or (meth) acrylate from the viewpoint of adhesion to the fine uneven structure. Specific examples of such compounds include "KBM" series, "KBE" series, "X" series manufactured by Shin-Etsu Chemical Industry Co., Ltd., "BYK" series manufactured by Big Chem Japan, "TEGO Rad" series manufactured by Ebonic Degussa Japan , "FG" series manufactured by Floro Technologies, "FS" series, and the like.

The material of the surface treatment layer can be applied to the cured article by a general method such as dip, spray, brush coating, or spin coating. Further, in order to improve the adhesion between the surface treatment layer and the cured layer having the fine uneven structure, it is preferable to perform the pre-treatment of the fine uneven structure region. Examples of the pretreatment include introduction of a functional group to the surface of the fine uneven structure by silica deposition or plasma, coating of a primer containing a compound having good reactivity with the surface treatment layer, and the like. The thickness of the surface treatment layer is preferably 100 nm or less from the viewpoint of maintaining the antireflection performance of the fine uneven structure. The existence of the surface treatment layer can be confirmed from the fact that the spectrum changes according to the angle of incidence in the angular variable ATR measurement or from the cross section observation by TEM.

(Fourth Embodiment)

Hereinafter, this embodiment will be described in detail.

The laminate according to the present embodiment is a laminate having a surface layer having a fine concavo-convex structure on its surface. The surface layer has a modulus of elasticity of less than 200 MPa and a water contact angle of the surface layer of 25 or less.

Wherein the surface layer contains a cured product of the active energy ray-curable resin composition, wherein the cured product of the active energy ray-curable resin composition is a mixture of 5 to 55 parts by mass of multifunctional (meth) acrylate having three or more functional groups and 5 to 55 parts by mass of polyethylene glycol diacrylate (The sum of the polymerizable components is 100 parts by mass) comprising 45 to 95 parts by mass of an ethylene glycol (the average repeating unit of ethylene glycol is 6 to 40). The laminate according to the present embodiment can easily remove stains without using water or alcohol on its surface, and is excellent in antifouling property.

1 is a longitudinal sectional view showing an example of a laminate according to the present embodiment. In the laminate 10 shown in Fig. 1, a surface layer 12 is formed on a transparent substrate 11 to be described later. A fine concavo-convex structure is formed on the surface of the surface layer 12. In addition, the surface layer 12 includes a cured product of the active energy ray-curable resin composition.

In the micro concavo-convex structure according to the present embodiment, the interval (pitch) w1 between adjacent convex portions 13 in Fig. 1 is preferably equal to or smaller than the wavelength of visible light, more preferably 100 nm or more and 300 nm or less, More preferably 150 nm or more and 250 nm or less, and particularly preferably 170 nm or more and 230 nm or less. In particular, when the pitch is 150 nm or more, even if the elastic modulus of the surface layer is less than 200 MPa, it is possible to further prevent the projections 13 from being joined together. Particularly, when the pitch is 250 nm or less, the scattering of visible light is further suppressed because it is sufficiently smaller than the wavelength of visible light, so that it can be suitably used as an anti-reflection article. On the other hand, in the present embodiment, "wavelength of visible light" means a wavelength of 400 nm. The interval between the adjacent convex portions indicates the interval w1 from the front end 13a of the convex portion to the front end 13a of the adjacent convex portion in Fig.

In the fine concavo-convex structure according to the present embodiment, the height d1 of the convex portion 13 in Fig. 1 is preferably 100 nm or more, more preferably 120 nm or more, more preferably 150 nm or more, Particularly preferred. When the height d1 of the convex portion 13 is 100 nm or more, the minimum reflectance does not rise or the reflectance at a specific wavelength does not rise. Even when the laminate is used as an antireflection article, sufficient antireflection . The upper limit of the height d1 of the convex portion 13 is not particularly limited, but may be, for example, 1 mu m or less. On the other hand, the height of the convex portion indicates the vertical distance d1 from the front end 13a of the convex portion to the bottom portion 14a of the adjacent concave portion in Fig.

It is preferable that the aspect ratio (height d1 of convex portion 13 / interval w1 between adjacent convex portions 13) is 0.5 to 5.0, more preferably 0.6 to 2.0, and more preferably 0.7 to 1.5 , More preferably from 0.8 to 1.2. When the aspect ratio is larger than 0.5, sufficient antireflection properties can be obtained even when the laminate is used as an antireflection article without increasing the minimum reflectance or increasing the reflectance at a specific wavelength. When the aspect ratio is smaller than 5.0, since the convex portion is hard to be broken even when rubbed, the scratch resistance is improved and sufficient antireflection property is exhibited.

On the other hand, the interval between the adjacent convex portions and the height of the convex portions were measured by using a scanning electron microscope (trade name: "JSM-7400F", manufactured by Nippon Denshoku) after platinum was deposited for 10 minutes on the fine convex- And a voltage of 3.00 kv, respectively.

The elastic modulus of the surface layer according to the present embodiment is less than 200 MPa. When the modulus of elasticity is 200 MPa or more, the fine concavo-convex structure of the surface layer becomes hard, and the contamination entering the concave portion can not be sufficiently pushed out, resulting in poor antifouling property. The elastic modulus of the surface layer is preferably 40 MPa or more and 180 MPa or less, more preferably 60 MPa or more and 170 MPa or less, further preferably 90 MPa or more and 160 MPa or less, and particularly preferably 100 MPa or more and 150 MPa or less. When the elastic modulus of the surface layer is 40 MPa or more, it is possible to prevent projections of the convex portions of the fine concavo-convex structure from being united. Particularly, when the surface layer has a modulus of elasticity of 90 MPa or more, the micro concavo-convex structure is sufficiently rigid so that the projections of the convex portions can be further prevented. In particular, when the elastic modulus of the surface layer is 150 MPa or less, the fine concavo-convex structure is sufficiently soft so that the fine concavo-convex structure can be freely deformed, so that contamination in the concavity can be removed more easily and the antifouling property is improved.

On the other hand, the elastic modulus of the surface layer is a value measured by the following method. The surface of the surface layer was subjected to a load while increasing the load under the condition of 50 mN / 10 seconds using "FISCHERSCOPE (R) HM2000" (trade name, manufactured by Fisher Co., Ltd.) and maintained at 50 mN for 60 seconds. (Unloading). Calculate the modulus of elasticity by extrapolation using the point at which 65% and 95% of the load is applied. Or, by using a Teflon sheet having a thickness of 500㎛ as a spacer, sheathed material of active energy ray curable resin composition of the surface layer of the two sheets of glass, the integrated light amount of irradiation was irradiated with ultraviolet rays with energy of 3000mJ / cm ² active energy ray-curable The resin composition may be photo-cured to prepare a cured product of an active energy ray-curable resin composition having a thickness of 500 mu m and the elastic modulus may be calculated by measuring the irradiation surface of the cured product in the same manner as described above.

The water contact angle of the surface layer according to the present embodiment is 25 DEG or less, preferably 20 DEG or less, more preferably 15 DEG or less, and most preferably 10 DEG or less. When the water contact angle of the surface layer is 25 DEG or less, the surface of the laminate is hydrophilized, and the adhered dirt can be wiped off with water as described in Japanese Patent 4689718. [ The lower the water contact angle of the surface layer is, the lower the water contact angle is, and the lower limit thereof is not particularly limited, but may be 1 deg. Or more, for example, and 3% or more is preferable.

On the other hand, the water contact angle of the surface layer is a value obtained by dropping 1 mu l of water on the surface of the surface layer using an automatic contact angle measuring apparatus (manufactured by KRUSS) and calculating the contact angle after 7 seconds by the? / 2 method.

The laminate according to the present embodiment may include a substrate. For example, the base material 11 may be provided adjacent to the surface layer 12 like the layered body 10 shown in Fig.

The active energy ray curable resin composition according to the present embodiment preferably contains a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer, and is preferably one which is cured by a polymerization initiator . In addition, the active energy ray-curable resin composition according to the present embodiment may contain a non-reactive polymer.

The active energy ray curable resin composition according to the present embodiment contains 5 to 55 parts by mass of a trifunctional or higher polyfunctional (meth) acrylate, 45 to 95 parts by mass of polyethylene glycol diacrylate (average repeating unit of ethylene glycol is 6 to 40) (Provided that the total amount of the polymerizable components is 100 parts by mass). Thus, the elastic modulus of the surface layer can be made less than 200 MPa. On the other hand, in the present specification, (meth) acrylate refers to acrylate or methacrylate. The polymerizable component means a compound having a polymerizable functional group.

The multifunctional (meth) acrylate having three or more functional groups is not particularly limited, but is preferably a multifunctional (meth) acrylate having four or more functional groups, and more preferably a multifunctional (meth) acrylate having five or more functional groups. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hydroxy penta (meth) acrylate, A condensation reaction mixture of dipentaerythritol hexa (meth) acrylate (e.g., Kayarad DPEA (trade name, manufactured by Nippon Kayaku)), a molar ratio of succinic acid / trimethylolethane / acrylic acid of 1: 2: 4, (E.g., EBECRYL 81 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.)), urethane acrylates (e.g., EBECRYL220, EBECRYL1290, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL8301, KRM8200 (For example, EBECRYL450, EBECRYL657, EBECRYL800, manufactured by Daicel-Cytec Co., Ltd.), modified epoxy acrylates such as EBECRYL3416 EBECRYL8 10 (trade name, manufactured by Daicel-Cytec Co., Ltd.), ethylene oxide-modified dipentaerythritol hexaacrylate (e.g., Kayarad DPEA-12 And monomers in which ethylene oxide or propylene oxide is added to the above monomers such as DPEA-18 (trade name, manufactured by Dai-ichi Kogyo Pharmaceutical Co., Ltd.) These may be used alone, or two or more of them may be used in combination.

The multifunctional (meth) acrylate having three or more functional groups contained in the polymerizable component is preferably 5 to 55 parts by mass, more preferably 10 to 50 parts by mass, and most preferably 20 to 50 parts by mass when the total of the polymerizable components is 100 parts by mass By mass to 45% by mass, and particularly preferably from 25 to 40% by mass. When it is less than 5 parts by mass, there is a case that the elastic modulus enough to transfer the fine concavo-convex structure to the surface layer can not be given. When the amount exceeds 55 parts by mass, the elastic modulus of the surface layer can not be made less than 200 MPa, which makes it hard to push out the contamination. On the other hand, particularly when the amount is 25 parts by mass or more, a sufficient elastic modulus is given to the surface layer, so that the projections of the convex portions of the fine concavo-convex structure can be further suppressed. Particularly when the amount is 45 parts by mass or less, the lowering of the mobility of the convex portion is further suppressed, and high stainproofness is exhibited.

(Average repeating unit of ethylene glycol: 13) manufactured by Aronix M-260 (manufactured by Toa Kagaku Kogyo Co., Ltd.), polyethylene glycol diacrylate (average repeating unit of ethylene glycol of 6 to 40) as bifunctional (meth) A-400 (average repeating unit of ethylene glycol: 9), A-600 (average repeating unit of ethylene glycol: 14), A-1000 (average repeating unit of ethylene glycol: Ltd.) and the like. These may be used alone, or two or more of them may be used in combination. By including the polyethylene glycol diacrylate unit in the polymer, it is possible to increase the molecular mobility of the cured product contained in the surface layer and to push out the contamination in the recess.

The average repeating unit of ethylene glycol present in the polyethylene glycol diacrylate is preferably 6 to 40, more preferably 9 to 30, further preferably 10 to 25, particularly preferably 12 to 20. When the average repeating unit of ethylene glycol is less than 6, the water contact angle of the surface layer can not be 25 DEG or less and sufficient antifouling property may not be obtained. On the other hand, when the average repeating unit of ethylene glycol exceeds 40, compatibility with the trifunctional or higher polyfunctional (meth) acrylate may be insufficient.

The amount of the polyethylene glycol diacrylate contained in the polymerizable component is preferably 45 to 95 parts by mass, more preferably 50 to 85 parts by mass, more preferably 53 to 80 parts by mass Still more preferably from 55 to 75 parts by mass. If it is less than 45 parts by mass, the elastic modulus of the surface layer may not be less than 200 MPa. When the amount is more than 95 parts by mass, the modulus of elasticity to such an extent that the fine concavo-convex structure can be transferred to the surface layer may not be maintained. On the other hand, in particular, when the amount is 55 parts by mass or more, sufficient convective motion is imparted to the convex portion, thereby exhibiting sufficient antifouling property. Particularly when the amount is 75 parts by mass or less, the decrease in the modulus of elasticity is further suppressed, and the projections of the convex portions can be further restrained.

The polymerizable component may further contain a monofunctional monomer. The monofunctional monomer is not particularly limited as long as it is compatible with the trifunctional or higher polyfunctional (meth) acrylate and the polyethylene glycol diacrylate. Examples of monofunctional monomers include monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-20G, M-90G and M-230G (trade names, available from Shin- Nakamura Chemical Co., (Meth) acrylates having a hydroxyl group in an ester group such as a hydroxyalkyl (meth) acrylate, monofunctional acrylamides, methacrylamide propyltrimethylammonium methylsulfate, methacryloyloxyethyl tri And hydrophilic monofunctional monomers such as cationic monomers such as methylammonium methylsulfate. These may be used alone or in combination of two or more.

When the total amount of the polymerizable components is 100 parts by mass, the monofunctional monomer contained in the polymerizable component is preferably 0 to 20 parts by mass, more preferably 5 to 15 parts by mass. By introducing the mono-functional monomer unit into the polymer, the adhesion between the substrate and the surface layer is improved. When the content of the monofunctional monomer is 20 parts by mass or less, the content of the trifunctional or higher polyfunctional (meth) acrylate unit and the polyethylene glycol diacrylate unit in the polymer is not insufficient and sufficient stainproofing property is expressed .

Further, a polymer having a low degree of polymerization obtained by (co) polymerization of one or more of the above mono-functional monomers may be blended into the active energy ray curable resin composition. When the total amount of the polymerizable components is 100 parts by mass, the polymer having the low polymerization degree may be blended in the active energy ray curable resin composition, for example, 0 to 35 parts by mass. Examples of the polymer having a low degree of polymerization include monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group and 40/60 copolymerized oligomers of methacrylamide propyltrimethylammonium methylsulfate (trade name: " MG polymer " (Manufactured by MRC Unitech Co., Ltd.).

In addition, the active energy ray-curable resin composition may contain fine particles such as an antistatic agent, a release agent, an ultraviolet absorber, colloidal silica and the like in addition to the above-mentioned various monomers and polymers having a low degree of polymerization. The active energy ray curable resin composition may contain a viscosity adjusting agent such as acryloylmorpholine or vinyl pyrrolidone, and an adhesion improver such as acryloyl isocyanate which improves the adhesion to the substrate.

When the active energy ray curable resin composition contains a releasing agent, good releasability can be maintained when the layered product according to the present embodiment is continuously produced. Particularly, in the case of using an anodized alumina mold, the mold release agent tends to be adsorbed on the surface of the mold, because the (poly) oxyalkylene alkyl phosphate compound and alumina interact with each other.

JP-506H "manufactured by Joho Chemical Industry Co., Ltd.," Moldwiz INT-1856 "manufactured by Axel Co., Ltd.," TDP-10 "manufactured by Nikko Chemicals Co., Ltd. as a commercially available product of (poly) oxyalkylene alkyl phosphate, DDP-8, DDP-8, DDP-8, DDP-8, DDP-6, DDP- TLP-4 "," TCP-5 "and" DLP-10 "(trade names, trade names). The release agents contained in the active energy ray-curable resin composition may be used alone or in combination of two or more.

The ratio of the releasing agent contained in the active energy ray-curable resin composition is preferably 0.01 to 2.0 parts by mass, more preferably 0.05 to 0.2 parts by mass, per 100 parts by mass of the polymerizable component. When the proportion of the release agent is 0.01 parts by mass or more, the releasability from the mold of the article having the fine uneven structure on the surface is good. On the other hand, when the proportion of the releasing agent is 2.0 mass% or less, the adhesion between the cured product of the active energy ray-curable resin composition and the base material is good, and the hardness of the cured product is adequate, whereby the fine uneven structure can be sufficiently retained.

Specific examples of the active energy ray used for curing the active energy ray-curable resin composition include visible rays, ultraviolet rays, electron beams, plasma, and infrared rays.

Further, the active energy ray-curable resin composition may be cured by using a combination of photo-curing and thermal curing.

As described above, the laminate according to the present embodiment is provided with a surface layer containing a cured product of an active energy ray-curable resin composition having a fine concavo-convex structure on its surface, the surface layer having a modulus of elasticity of less than 200 MPa, And therefore, the antifouling property is excellent. Further, when the interval between adjacent convex portions of the fine concavo-convex structure is equal to or smaller than the wavelength (400 nm) of visible light, the laminate according to this embodiment is particularly suitable for use in antireflection articles . When the height of the convex portion is 100 nm or more, the antireflection property is more excellent.

Further, the antireflection article, the image device, and the touch panel according to the present embodiment are excellent in antireflection performance and antifouling property because they include the laminate according to the present embodiment. Particularly, when the laminated body according to the present embodiment is provided on the outermost surface of the antireflective article, the image device, and the touch panel, contamination of sebum or the like adhered at the time of use tends to be difficult to drop, have.

(Embodiment 5)

Hereinafter, this embodiment will be described in detail.

1 is a schematic cross-sectional view showing an example of the configuration of the layered product 10 according to the present embodiment. In Fig. 1, a surface layer 12 made of a cured product of an active energy ray-curable resin composition is formed on the surface of a base material 11 having transparency. In the laminate 10, a fine concavo-convex structure is formed on the surface of the surface layer 12.

In the laminate of the present embodiment, the water contact angle of the surface layer of the portion where the fine concavo-convex structure is formed is preferably 130 deg. Or more, more preferably 135 deg. When the water contact angle of the surface layer is 130 DEG or more, the surface energy is sufficiently small so that the contamination can be easily wiped off. Further, when the water contact angle of the surface layer is further 135 DEG or more, adhesion of the contamination can be suppressed because the surface energy is sufficiently small. The upper limit of the water contact angle of the surface layer is not particularly limited, but is preferably 150 占 or less, and more preferably 145 占 or less.

In the laminate of the present embodiment, the elastic modulus of the surface of the micro concavo-convex structure, that is, the elastic modulus of the surface layer is preferably less than 200 MPa and preferably 50 to 100 MPa. When the elastic modulus of the surface layer is less than 200 MPa, the fine concavo-convex structure is smooth, so that contamination in the concave portion can be pushed out. When the elastic modulus of the surface layer is 50 MPa or more, the fine concavo-convex structure is sufficiently rigid so that the projections of the convex portions can be prevented effectively. If the elastic modulus of the surface layer is 100 MPa or less, the fine concavo-convex structure is sufficiently soft, so that the fine concavo-convex structure can be freely deformed, and contamination in the concavity can be easily removed.

In the laminate of the present embodiment, the surface layer is composed of a cured product of the active energy ray-curable resin composition. The active energy ray curable resin composition preferably contains 1 to 55 parts by mass of a trifunctional or higher polyfunctional (meth) acrylate (A), 10 to 95 parts by mass of a bifunctional (meth) acrylate (B) (Meth) acrylate (C) in an amount of 3 to 85 parts by mass. On the other hand, the silicone (meth) acrylate (C) is excluded from the trifunctional or higher polyfunctional (meth) acrylate (A) and the bifunctional (meth) acrylate (B).

Here, the polyfunctional (meth) acrylate having three or more functional groups means at least three groups selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) ≪ / RTI > The bifunctional (meth) acrylate refers to a compound having two groups selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) in the molecule it means.

The multifunctional (meth) acrylate (A) having three or more functional groups is preferably four or more functional groups, and more preferably five or more functional groups. Examples of the multifunctional (meth) acrylate (A) having three or more functional groups include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra Condensation reaction product of dipentaerythritol hydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4, urethane acrylates , Polyether acrylates, modified epoxy acrylates, and polyester acrylates. Examples of the urethane acrylates include "EBECRYL220", "EBECRYL1290", "EBECRYL1290K", "EBECRYL5129", "EBECRYL8210", "EBECRYL8301" and "KRM8200" manufactured by Daicel-Cytec. Examples of the polyether acrylates include EBECRYL81 from Daicel-Cytec. As the modified epoxy acrylates, "EBECRYL3416" manufactured by Daicel-Cytec Co., Ltd. may be mentioned. EBECRYL850 "," EBECRYL810 "," EBECRYL811 "," EBECRYL812 "," EBECRYL1830 "," EBECRYL845 "," EBECRYL846 "and" EBECRYL846 "manufactured by Daicel-Cytec Co., &Quot; EBECRYL1870 ". Examples of the multifunctional (meth) acrylate (A) having three or more functional groups include monomers obtained by adding ethylene oxide or propylene oxide to the above monomers. These polyfunctional (meth) acrylates (A) may be used alone or in combination of two or more.

When the total amount of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass, the multifunctional (meth) acrylate (A) having three or more functionalities is preferably 1 to 55 parts by mass, more preferably 11 to 30 parts by mass desirable. By setting the content of the trifunctional or higher polyfunctional (meth) acrylate (A) to 1 part by mass or more, a modulus of elasticity capable of transferring the micro concavo-convex structure to the surface layer can be imparted. Further, by setting the content of the trifunctional or higher polyfunctional (meth) acrylate (A) to 55 parts by mass or less, an increase in the modulus of elasticity of the surface layer can be suppressed. As a result, contamination can be easily pushed out from the concave portion, and sufficient antifouling properties can be imparted to the laminate. When the amount is 11 parts by mass or more, a good modulus of elasticity can be imparted to the surface layer, and the projections of the convex portions in the fine concavo-convex structure can be suppressed. When the content is 30 parts by mass or less, the decrease in the mobility of the convex portion is suppressed, and the antifouling property capable of easily removing the contamination can be effectively exhibited without using water or alcohol. On the other hand, in the present specification, the projecting unity of the projections or projections means that the projections or projections adjacent to each other are formed into one.

Examples of the bifunctional (meth) acrylate (B) include bifunctional acrylates having polyethylene glycol, bifunctional acrylates having polypropylene glycol and polyalkylene glycols such as bifunctional acrylates having polybutylene glycol ≪ / RTI > is preferred. Specific examples of the bifunctional acrylates having polyethylene glycol include Aronix M-240, Aronix M-260 (manufactured by DOA Corporation), NK ester AT-20E and NK ester ATM-35E (manufactured by Shin Nakamura Chemical Co., . Specific examples of bifunctional acrylates having polypropylene glycol include APG-400 and APG-700 (manufactured by Shin Nakamura Chemical Co., Ltd.). Specific examples of bifunctional acrylates having polybutylene glycol include A-PTMG-650 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. By using a bifunctional acrylate having a polyalkylene glycol as the bifunctional (meth) acrylate (B), the elastic modulus of the surface layer is suppressed and the stain is easily pushed out from the concave portion, thereby effectively exhibiting stain resistance. Among the bifunctional acrylates having a polyalkylene glycol, polyethylene glycol diacrylate is suitably used in that a more excellent antifouling property is obtained. By using polyethylene glycol diacrylate as the bifunctional (meth) acrylate (B), the molecular mobility of the resin in the surface layer is improved, so that contamination in the recess can be more easily pushed out, and good antifouling properties are exhibited.

The total number of the average repeating units of the polyethylene glycol chain present in one molecule of the polyethylene glycol diacrylate is preferably 6 to 40, more preferably 9 to 30, and even more preferably 12 to 20. When the average repeating unit of the polyethylene glycol chain is 6 or more, the mobility of the molecule is maintained and good antifouling property is expressed. When the average repeating unit of the polyethylene glycol chain is 40 or less, compatibility with the trifunctional or higher polyfunctional (meth) acrylate (A) is improved. Among the bifunctional acrylates having polyalkylene glycol, polypropylene glycol diacrylate and polybutylene glycol diacrylate are also suitably used from the viewpoint of compatibility. (Meth) acrylate such as silicone di (meth) acrylate having a low hydrophilicity can be obtained by using polypropylene glycol diacrylate or polybutylene glycol diacrylate as the bifunctional (meth) acrylate (B) ) Is improved, and a transparent active energy ray-curable resin composition can be obtained. These bifunctional (meth) acrylates (B) may be used alone or in combination of two or more. Also, polyethylene glycol and polypropylene glycol diacrylate and / or polybutylene glycol diacrylate are preferably used in combination in view of compatibility between antifouling property and compatibility.

The bifunctional (meth) acrylate (B) is preferably 10 to 95 parts by mass, and more preferably 20 to 70 parts by mass, when the total amount of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass . When the content of the bifunctional (meth) acrylate (B) is 10 parts by mass or more, an increase in the modulus of elasticity of the surface layer is suppressed, and the stain is easily pushed out from the concave portion. By setting the content of the bifunctional (meth) acrylate (B) to 95 parts by mass or less, it is possible to maintain the modulus of elasticity such that the fine concavo-convex structure can be transferred to the surface layer. When the content is 20 parts by mass or more, mobility can be imparted to the convex portion, and antifouling property is effectively exhibited. When the amount is 70 parts by mass or less, deterioration of the modulus of elasticity is suppressed, and the projections of the convex portions can be suppressed.

(CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ )) at the side chain and / or the end of the compound having an organosiloxane structure, and the silicon (meth) acrylate (C) CO-) as long as it is a compound having at least one group selected from the group consisting of The silicone (meth) acrylate (C) is preferably selected from the viewpoint of compatibility of the trifunctional or higher polyfunctional (meth) acrylate (A) with the bifunctional (meth) acrylate (C) ) As the acrylate (C), it is preferable to use a compound having a compatible segment contributing to compatibility with (A) and (B). Examples of the compatible segment include a polyalkylene oxide structure, a polyester structure, and a polyamide structure. These compatibilizing segments may be contained singly in the silicone (meth) acrylate (C), or may contain two or more species. Further, the silicone (meth) acrylate (C) may be diluted in view of handleability. As the diluent, it is preferable that the diluent has reactivity in terms of bleeding out from the cured product. (Meth) acrylate (C) by mixing a trifunctional or higher polyfunctional (meth) acrylate (A) or a bifunctional (meth) acrylate (B) Can be improved.

Specific examples of such silicone (meth) acrylate (C) include Sirea plain series manufactured by Jitsu Co., Ltd., silicone diacrylate " X-22-164 ", Shin- 160K, " BYK-3500 " manufactured by Big Chem Japan Co., Ltd., BYK-3570, and TEGO Rad series manufactured by Ebonic Degussa Japan. These silicone (meth) acrylates (C) may be used alone or in combination of two or more.

When the total amount of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass, the amount of the silicone (meth) acrylate (C) is preferably 3 to 85 parts by mass, more preferably 5 to 70 parts by mass, By mass to 70 parts by mass, and particularly preferably 45 to 65 parts by mass. When the content of the silicone (meth) acrylate (C) is 3 parts by mass or more, the water contact angle of the surface layer having the fine uneven structure tends to become 130 degrees or more, and the antifouling property is imparted to the laminate. Further, by setting the content of the silicone (meth) acrylate (C) to 85 parts by mass or less, a modulus of elasticity capable of transferring the fine concavo-convex structure to the surface layer can be imparted. When the amount is 5 parts by mass or more, the water contact angle of the surface layer tends to be 135 deg. Or more, and the antifouling property of the laminate is improved. When the amount is 70 parts by mass or less, the viscosity of the active energy ray-curable resin composition is suppressed and the handling property is improved. When the amount is more than 45 parts by mass, compatibility with components (A) and (B) in the active energy ray curable resin composition is improved, and the water repellency of the surface layer and the flexibility of the projections are improved, Excellent antifouling property is expressed. When the amount is 65 parts by mass or less, it is possible to suppress the decrease in the modulus of elasticity of the surface layer and suppress the unevenness of protrusions of the fine unevenness structure.

The active energy ray curable resin composition may further contain a monofunctional monomer. The monofunctional monomer is preferably selected in consideration of the compatibility with the trifunctional or higher polyfunctional (meth) acrylate (A) and the bifunctional (meth) acrylate (B), and from this viewpoint, Monomolecular (meth) acrylates having a polyethylene glycol chain in the group, mono-functional (meth) acrylates having a hydroxyl group in an ester group such as a hydroxyalkyl (meth) acrylate, mono-functional acrylamides, Cationic monomers such as propyl trimethylammonium methylsulfate and methacryloyloxyethyl trimethylammonium methylsulfate, and the like, can be preferably exemplified. Specific examples of monofunctional monomers include monomolecular (meth) acrylates such as "M-20G", "M-90G" and "M-230G" (manufactured by Shin Nakamura Chemical Co., Ltd.).

In addition, a viscosity adjuster such as acryloylmorpholine or vinylpyrrolidone or an adhesion improver such as acryloyl isocyanate which improves the adhesion to a transparent substrate may be added to the active energy ray curable resin composition .

The content of the mono-functional monomer in the active energy ray-curable resin composition is preferably from 0.1 to 20 parts by mass, more preferably from 5 to 15 parts by mass, based on 100 parts by mass of the total of the polymerizable components in the active energy ray- More preferable. By including the monofunctional monomer, the adhesion between the substrate and the surface layer (active energy ray curable resin) is improved. (Meth) acrylate (A) and the bifunctional (meth) acrylate (B) can be adjusted by adjusting the content of the monofunctional monomer to 20 parts by mass or less to sufficiently exhibit the antifouling property . The monofunctional monomers may be used singly or in combination of two or more.

Further, a polymer (oligomer) having a low degree of polymerization obtained by polymerizing one or more monofunctional monomers may be added to the active energy ray curable resin composition. Specific examples of the polymer having such a low polymerization degree include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group (for example, "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd.), methacrylamide propyl tri 40/60 copolymer oligomer of methylammonium methylsulfate (e.g., " MG polymer ", manufactured by MRC Unitech Co., Ltd.).

The active energy ray curable composition may contain fine particles such as an antistatic agent, a releasing agent, an ultraviolet absorber, and colloidal silica, in addition to the various monomers and polymers having a low degree of polymerization described above.

The active energy ray curable resin composition may contain a release agent. When the active energy ray-curable resin composition contains a releasing agent, good releasability can be maintained when the laminate is continuously produced. Examples of the release agent include (poly) oxyalkylene alkyl phosphoric acid compounds. Particularly, in the case of using an anodized alumina mold, the (poly) oxyalkylene alkyl phosphate compound and alumina interact with each other, so that the mold release agent is likely to be adsorbed on the surface of the mold.

JP-506H "(trade name) manufactured by JOHOKU CHEMICAL INDUSTRIAL CO., LTD.," MoldWiz INT-1856 "(trade name) manufactured by Axel Corporation, a product of Nikko Chemicals Co., TDP-8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP- DDP-2 "," TLP-4 "," TCP-5 ", and" DLP-10 "(trade names).

The release agents contained in the active energy ray-curable resin composition may be used alone or in combination of two or more.

The content of the releasing agent contained in the active energy ray-curable resin composition is preferably 0.01 to 2.0 parts by mass, more preferably 0.05 to 0.2 parts by mass based on 100 parts by mass of the polymerizable component. When the content of the releasing agent is 0.01 parts by mass or more, the releasability from the mold of the article having the fine uneven structure on the surface is good. On the other hand, when the ratio of the releasing agent is 2.0 parts by mass or less, the adhesion between the cured product of the active energy ray-curable resin composition and the base material is good, and the hardness of the cured product is adequate, whereby the fine uneven structure can be sufficiently retained.

The active energy ray curable resin composition in the present embodiment may suitably contain a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer, It hardens. In addition, the active energy ray-curable resin composition may include a non-reactive polymer.

Since the laminate of the present embodiment is a laminate having a surface layer having excellent antifouling properties, which can easily remove contamination, the laminate of the present embodiment can be used as an antireflective article, an image display, It is difficult to cause contamination of sebum or the like adhered at the time of use, and it is easy to fall off, and a good antireflection performance can be exhibited. In addition, since contamination can be easily removed without using water or alcohol on the surface, an article excellent in practical use can be obtained.

(Embodiment 6)

Hereinafter, this embodiment will be described in detail.

1 is a schematic cross-sectional view showing an example of the configuration of the layered product 10 according to the present embodiment. 1, a surface layer 12 made of a cured product of an active energy ray-curable resin composition is formed on the surface of a base material 11 having transparency, and a surface treatment layer 13 is provided on the surface of the surface layer 12.

In the laminate of the present embodiment, the elastic modulus of the surface of the laminate, that is, the modulus of elasticity of the fine uneven structure layer including the surface treatment layer and the surface layer is preferably 2000 MPa or less, more preferably 200 MPa or less, and more preferably 50 to 100 MPa . If the modulus of elasticity of the fine uneven structure layer is 2000 MPa or less, the fine uneven structure is smooth, so that contamination entering the recess can be moved with a small external force. When the modulus of elasticity of the fine uneven structure layer is 200 MPa or less, the fine uneven structure is softer, so that contamination in the recess can be pushed out with an extremely small external force. When the modulus of elasticity of the fine uneven structure layer is 50 MPa or more, the unevenness of the convex portions of the fine uneven structure can be effectively prevented. When the elastic modulus of the surface layer is 100 MPa or less, the fine concavo-convex structure is sufficiently smooth, so that the fine concavo-convex structure can be freely deformed with an extremely small external force, and contamination in the concavity can be easily removed. On the other hand, in the present specification, the term " unity of protrusions or protrusions " means that the adjacent protrusions or protrusions are combined to form one.

In the laminate of the present embodiment, the surface layer is composed of a cured product of the active energy ray-curable resin composition. The active energy ray curable resin composition contains 25 to 70 parts by mass of a trifunctional or higher polyfunctional (meth) acrylate (A) and 30 to 75 parts by mass of a bifunctional (meth) acrylate (B) Provided that the total of the polymerizable components is 100 parts by mass).

Here, the polyfunctional (meth) acrylate having three or more functional groups means at least three groups selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) ≪ / RTI > The bifunctional (meth) acrylate refers to a compound having two groups selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) in the molecule it means.

The multifunctional (meth) acrylate (A) having three or more functional groups is preferably four or more functional groups, and more preferably five or more functional groups. Examples of the multifunctional (meth) acrylate (A) having three or more functional groups include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra Condensation reaction product of dipentaerythritol hydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / (meth) acrylic acid molar ratio 1: 2: 4, urethane (Meth) acrylates, polyether (meth) acrylates, modified epoxy (meth) acrylates, polyester (meth) acrylates and silicone (meth) acrylates. Examples of the urethane (meth) acrylates include "EBECRYL220", "EBECRYL1290", "EBECRYL1290K", "EBECRYL5129", "EBECRYL8210", "EBECRYL8301" and "KRM8200" manufactured by Daicel-Cytek. Examples of the polyether (meth) acrylates include EBECRYL81 from Daicel-Cytec. As the modified epoxy (meth) acrylates, "EBECRYL3416" manufactured by Daicel-Cytec Co., Ltd. may be mentioned. Examples of polyester (meth) acrylates include "EBECRYL450", "EBECRYL657", "EBECRYL800", "EBECRYL810", "EBECRYL811", "EBECRYL812", "EBECRYL830", "EBECRYL845" EBECRYL846 ", and " EBECRYL1870 ". As the silicone (meth) acrylates, "BYK-3570" manufactured by Big Chem Japan Co., Ltd. and TEGO Rad series manufactured by Ebonic Degussa Japan are suitably used. Examples of the trifunctional or more multifunctional (meth) acrylate (A) include monomers in which ethylene oxide or propylene oxide is added to the above monomers. These polyfunctional (meth) acrylates (A) may be used alone or in combination of two or more.

The trifunctional or more multifunctional (meth) acrylate (A) is 25 to 70 parts by mass when the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass. By setting the content of the trifunctional or higher polyfunctional (meth) acrylate (A) to 25 parts by mass or more, a modulus of elasticity capable of transferring the micro concavo-convex structure to the surface layer can be imparted. Further, by setting the content of the trifunctional or higher polyfunctional (meth) acrylate (A) to 70 parts by mass or less, an increase in the modulus of elasticity of the surface layer can be suppressed. As a result, contamination can be easily pushed out from the concave portion, and sufficient antifouling properties can be imparted to the laminate.

Examples of the bifunctional (meth) acrylate (B) include bifunctional acrylates having polyethylene glycol, bifunctional acrylates having polypropylene glycol and polyalkylene glycols such as bifunctional acrylates having polybutylene glycol ≪ / RTI > is preferred. Specific examples of the bifunctional acrylates having polyethylene glycol include Aronix M-240, Aronix M260 (manufactured by DOA Corporation), NK ester AT-20E and NK ester ATM-35E (manufactured by Shin Nakamura Chemical Co., Ltd.) . Specific examples of bifunctional acrylates having polypropylene glycol include APG-400 and APG700 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Specific examples of bifunctional acrylates having polybutylene glycol include A-PTMG-650 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. By using a bifunctional acrylate having a polyalkylene glycol as the bifunctional (meth) acrylate (B), the elastic modulus of the surface layer is suppressed and the stain is easily pushed out from the concave portion, thereby effectively exhibiting stain resistance. Among the bifunctional acrylates having a polyalkylene glycol, polyethylene glycol diacrylate is suitably used in that a more excellent antifouling property is obtained. By using polyethylene glycol diacrylate as the bifunctional (meth) acrylate (B), the molecular mobility of the resin in the surface layer is improved, so that contamination in the recess can be more easily exerted, and good antifouling properties are exhibited.

The total number of the average repeating units of the polyethylene glycol chain present in one molecule of the polyethylene glycol diacrylate is preferably 6 to 40, more preferably 9 to 30, and even more preferably 12 to 20. When the average repeating unit of the polyethylene glycol chain is 6 or more, the mobility of the molecule is maintained and good antifouling property is expressed. When the average repeating unit of the polyethylene glycol chain is 40 or less, compatibility with the trifunctional or higher polyfunctional (meth) acrylate (A) is improved. Among the bifunctional acrylates having polyalkylene glycol, polypropylene glycol diacrylate and polybutylene glycol diacrylate are also suitably used from the viewpoint of compatibility. (Meth) acrylate such as a silicone di (meth) acrylate having a low hydrophilicity, which will be described later, by using polypropylene glycol diacrylate or polybutylene glycol diacrylate as the bifunctional (meth) acrylate (B) And the transparent active energy ray-curable resin composition can be obtained. These bifunctional (meth) acrylates (B) may be used alone or in combination of two or more. Also, polyethylene glycol and polypropylene glycol diacrylate and / or polybutylene glycol diacrylate are preferably used in combination in view of compatibility between antifouling property and compatibility.

As the bifunctional (meth) acrylate (B), silicone (meth) acrylate is suitably used from the viewpoint that the surface free energy is small and the antifouling property is improved. Specific examples of the silicone (meth) acrylate include Sai Plain series manufactured by Jitsu Corporation, silicone diacrylate "X-22-164", "X-22-1602" manufactured by Shin-Etsu Chemical Co., &Quot; BYK-3500 " manufactured by Japan, and TEGO Rad series manufactured by Ebonic Degussa Japan are suitably used. These bifunctional (meth) acrylates (B) may be used alone or in combination of two or more.

The bifunctional (meth) acrylate (B) is 30 to 75 parts by mass when the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass. When the content of the bifunctional (meth) acrylate (B) is 30 parts by mass or more, an increase in the modulus of elasticity of the surface layer is suppressed, and the stain is easily pushed out from the concave portion. By reducing the content of the bifunctional (meth) acrylate (B) to 75 parts by mass or less, the decrease in the modulus of elasticity is suppressed and the unevenness of the convex portions can be suppressed.

The active energy ray curable resin composition may further contain a monofunctional monomer. The monofunctional monomer is preferably selected in consideration of the compatibility with the trifunctional or higher polyfunctional (meth) acrylate (A) and the bifunctional (meth) acrylate (B), and from this viewpoint, Monomolecular (meth) acrylates having a polyethylene glycol chain in the group, mono-functional (meth) acrylates having a hydroxyl group in an ester group such as a hydroxyalkyl (meth) acrylate, mono-functional acrylamides, Cationic monomers such as propyl trimethylammonium methylsulfate and methacryloyloxyethyl trimethylammonium methylsulfate, and the like, can be preferably exemplified. Specific examples of the monovalent monomer include "M-20G", "M-90G", "M-230G" (manufactured by Shin Nakamura Chemical Co., Ltd.) and the like. In addition, from the viewpoint of improving the antifouling property, alkyl mono (meth) acrylate, silicone (meth) acrylate and alkyl fluoro (meth) acrylate are suitably used. Specific examples of such mono-functional monomers include Nemic analogue blends such as "Blemmer LA", "Blumer CA", "Blemmer SA", "X-24-8201" -174DX ", produced by Exflora Research Co., Ltd., and " C10GACRY "

In addition, a viscosity adjuster such as acryloylmorpholine or vinylpyrrolidone or an adhesion improver such as acryloyl isocyanate which improves the adhesion to a transparent substrate may be added to the active energy ray curable resin composition .

The content of the mono-functional monomer in the active energy ray-curable resin composition is preferably from 0.1 to 20 parts by mass, more preferably from 5 to 15 parts by mass, based on 100 parts by mass of the total of the polymerizable components in the active energy ray- More preferable. By including the monofunctional monomer, the adhesion between the substrate and the surface layer (active energy ray curable resin) is improved. (Meth) acrylate (A) and the bifunctional (meth) acrylate (B) can be adjusted by adjusting the content of the monofunctional monomer to 20 parts by mass or less to sufficiently exhibit the antifouling property . The monofunctional monomers may be used singly or in combination of two or more.

Further, a polymer (oligomer) having a low degree of polymerization obtained by polymerizing one or more monofunctional monomers may be added to the active energy ray curable resin composition. Specific examples of the polymer having such a low polymerization degree include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group (for example, "M-230G" manufactured by Shin-Nakamura Chemical Co., Ltd.), methacrylamide propyl tri 40/60 copolymer oligomer of methylammonium methylsulfate (e.g., " MG polymer ", manufactured by MRC Unitech Co., Ltd.).

The active energy ray curable composition may contain fine particles such as an antistatic agent, a releasing agent, an ultraviolet absorber, and colloidal silica, in addition to the various monomers and polymers having a low degree of polymerization described above.

The active energy ray curable resin composition may contain a release agent. When the active energy ray-curable resin composition contains a releasing agent, good releasability can be maintained when the laminate is continuously produced. Examples of the release agent include (poly) oxyalkylene alkyl phosphoric acid compounds. Particularly, in the case of using an anodized alumina mold, the mold release agent tends to be adsorbed on the surface of the mold, because the (poly) oxyalkylene alkyl phosphate compound and alumina interact with each other.

JP-506H "(trade name)," Moldwiz INT-1856 "(trade name) manufactured by Axel Co., Ltd. (trade name) manufactured by JOHOKU CHEMICAL CO., LTD., And" DDP-8 "," DDP-4 "," DDP-5 "," DDP- 2 "," TLP-4 "," TCP-5 ", and" DLP-10 "(trade names).

The release agents contained in the active energy ray-curable resin composition may be used alone or in combination of two or more.

The content of the releasing agent contained in the active energy ray-curable resin composition is preferably 0.01 to 2.0 parts by mass, more preferably 0.05 to 0.2 parts by mass based on 100 parts by mass of the polymerizable component. When the content of the releasing agent is 0.01 parts by mass or more, the releasability from the mold of the article having the fine uneven structure on the surface is good. On the other hand, when the ratio of the releasing agent is 2.0 parts by mass or less, the adhesion between the cured product of the active energy ray-curable resin composition and the base material is good, and the hardness of the cured product is adequate, whereby the fine uneven structure can be sufficiently retained.

In the laminate of the present embodiment, the water contact angle of the surface treatment layer is preferably 120 DEG or more, more preferably 130 DEG or more. When the water contact angle of the surface treatment layer is 120 DEG or more, the surface energy is sufficiently small so that the contamination can be easily wiped off. When the water contact angle of the surface treatment layer is 130 DEG or more, adhesion of the contamination can be suppressed because the surface energy is sufficiently small. The upper limit of the water contact angle of the surface treatment layer is not particularly limited, but is preferably 150 占 or less, more preferably 145 占 or less. As such a surface treatment layer exhibiting such water repellency, a compound having an alkyl group, a polydimethylsiloxane structure and an alkyl fluoride group is suitably used, and from the viewpoint of adhesion to a fine concavo-convex structure, silane, alkoxysilane, Methacrylate, and the like. Specific examples of such compounds include "KBM" series, "KBE" series, "X" series manufactured by Shin-Etsu Chemical Industry Co., Ltd., "BYK" series manufactured by Big Chem Japan, "TEGO Rad" series manufactured by Ebonic Degussa Japan , "FG" series manufactured by Floro Technologies, "FS" series, and the like.

The surface treatment layer can be coated by a general method such as dip, spray, brush, or spin coating. Further, in order to improve the adhesion between the surface treatment layer and the surface of the fine uneven structure, it is preferable to perform the pre-treatment on the fine uneven structure. Examples of the pretreatment include silica deposition, introduction of a functional group to the surface by plasma or the like, and coating of a primer containing a compound having good reactivity with the surface treatment layer. The thickness of the surface treatment layer is preferably 100 nm or less from the viewpoint of maintaining the antireflection performance of the fine concavo-convex shape. The surface treatment layer can be confirmed by the angle variable ATR measurement, the spectrum being changed with the incident angle, or the existence thereof from the cross section observation by TEM.

The active energy ray curable resin composition in the present embodiment may suitably contain a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer, It hardens. In addition, the active energy ray-curable resin composition may include a non-reactive polymer.

Since the laminate of the present embodiment is a laminate having a surface layer having excellent antifouling properties, which can easily remove contamination, the laminate of the present embodiment can be used as an antireflective article, an image display, It is difficult to cause contamination of sebum or the like adhered at the time of use, and it is easy to fall off, and a good antireflection performance can be exhibited. In addition, since contamination can be easily removed without using water or alcohol on the surface, an article excellent in practical use can be obtained.

(Seventh Embodiment)

Hereinafter, this embodiment will be described in detail.

1 is a schematic cross-sectional view showing an example of the configuration of the layered product 10 according to the present embodiment. In Fig. 1, a surface layer 12 made of a cured product of the active energy ray-curable composition is formed on the surface of a base material 11 having transparency. In the laminate 10, a fine concavo-convex structure is formed on the surface of the surface layer 12.

The layered product of this embodiment includes the compound (D) in which the surface layer is a cured product of the active energy ray curable composition and the active energy ray curable composition has the SH group. The term SH refers to a syringe, mercury, mercury, or sulfhydryl group. By incorporating the compound (D) having an SH group in the active energy ray-curable composition, a chemical bond between a sulfur atom and a sulfur atom or a carbon atom is obtained. In this case, since the elastic modulus can be lowered while maintaining the cross-link density of the cured product, flexibility can be imparted to the protrusions while maintaining the shape of the protrusions, so that the contamination remaining in the recesses can be removed.

In the laminate of the present embodiment, the surface layer is a cured product of the active energy ray curable composition, and the active energy ray curable resin composition contains 0 to 95 parts by mass of a multifunctional (meth) acrylate (A) (Meth) acrylate (C) in an amount of 0 to 75 parts by mass, and the SH group-containing compound (D) in an amount of 1 to 60 parts by mass (provided that the total of the polymerizable components is 100 parts by mass). On the other hand, the silicone (meth) acrylate (C) is excluded from the multifunctional (meth) acrylate (A) of two or more functions.

Here, the multifunctional (meth) acrylate (A) with two or more functional groups means a group selected from an acryloyl group (CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ ) CO-) Refers to a compound having at least two compounds in the molecule.

Examples of the multifunctional (meth) acrylate (A) having two or more functional groups include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxy (meth) acrylate, (Meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2- ) Propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) (Meth) acrylate, ethylene oxide adducts of bisphenol A, di (meth) acrylate, bis (3-hydroxyethyl) , Bifunctional monomers such as propylene oxide adduct di (meth) acrylate of bisphenol A, hydroxypivalic neopentyl glycol di (meth) acrylate, divinylbenzene and methylene bisacrylamide, pentaerythritol tri ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide Modified triacrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate (Meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Acrylate, and tetramethylolmethane tetra (meth) acrylate, bifunctional or higher urethane acrylates, and bifunctional or higher polyester acrylates. These may be used alone or in combination of two or more.

When the sum of the polymerizable components in the active energy ray-curable composition is 100 parts by mass, the multifunctional (meth) acrylate (B) having two or more functional groups is preferably 0 to 95 parts by mass, more preferably 25 to 90 parts by mass And particularly preferably 40 to 90 parts by mass. When the content of the multifunctional (meth) acrylate (A) is greater than or equal to 0 and less than or equal to 95 parts by mass, an excessive decrease in the modulus of elasticity can be suppressed and the shape of the projections can be maintained. In addition, when the multifunctional (meth) acrylate (A) having two or more functional groups is added to the composition, that is, when its content is more than 0 part by mass, the modulus of elasticity is easily suppressed and the shape of the projections can be easily maintained. When the content of the multifunctional (meth) acrylate (A) is more than 40 parts by mass, the decrease in the modulus of elasticity can be suppressed and the unevenness of the projections can be prevented more effectively. When the content of the multifunctional (meth) acrylate (A) is not more than 95 parts by mass, the modulus of elasticity is lowered, and the contamination can be more effectively removed. When the content is 90 parts by mass or less, the modulus of elasticity is sufficiently lowered, so that contamination of the concave portion can be more effectively removed. As a result, contamination can be easily pushed out from the concave portion, and sufficient antifouling properties can be imparted to the laminate.

(CH ₂ ═CHCO-) and a methacryloyl group (CH ₂ ═C (CH ₃ )) at the side chain and / or the end of the compound having an organosiloxane structure, and the silicon (meth) acrylate (C) CO-). ≪ / RTI > The silicone (meth) acrylate (C) is preferably selected from the viewpoint of compatibility with the multifunctional (meth) acrylate (A) It is preferable to use a compound having a compatible segment contributing to compatibility. Examples of the compatible segment include a polyalkylene oxide structure, a polyester structure, and a polyamide structure. These compatibilizing segments may be contained singly in the silicone (meth) acrylate (C), or may contain two or more species. Further, the silicone (meth) acrylate (C) may be diluted in view of handleability. As the diluent, it is preferable that the diluent has reactivity in terms of bleeding out from the cured product. The handling of the silicone (meth) acrylate (C) can also be improved by mixing the multifunctional (meth) acrylate (A) with the silicone (meth) acrylate (C).

Specific examples of such silicone (meth) acrylate (C) include Sai Plain series (trade name) manufactured by Jitosha Co., Ltd., silicone diacrylate "X-22-164" "BYK-3500", "BYK-3570" (all trade names), and TEGO Rad series (trade name) available from Ebonnic Degussa Japan Co. are commercially available. These silicone (meth) acrylates (C) may be used alone or in combination of two or more.

When the total amount of the polymerizable components in the active energy ray-curable composition is 100 parts by mass, the amount of the silicone (meth) acrylate (C) is preferably 0 to 75 parts by mass, more preferably 5 to 70 parts by mass. When the content of the silicone (meth) acrylate (C) is 0 parts by mass or more and 75 parts by mass or less, water repellency is imparted and the antifouling property is further improved. In addition, when silicone (meth) acrylate (C) is added to the composition, that is, when its content is more than 0 part by mass, water repellency is more effectively imparted and antifouling property is improved. When the content of the silicone (meth) acrylate (C) is 5 parts by mass or more, the surface energy of the surface layer is lowered and the contact angle with water is 130 ° or more, so that the antifouling property is further improved. When the content of the silicone (meth) acrylate (C) is 75 parts by mass or less, transparency is improved because compatibility with other components is improved. When the content of the silicone (meth) acrylate (C) is 70 parts by mass or less, the viscosity of the active energy ray curable composition is suppressed and the handling property is improved.

The compound (D) containing an SH group is not particularly limited as long as it is a compound containing an SH group, but it is preferably a compound containing two or more SH groups in order to increase the cross-linking density of the surface layer and maintain the strength. From the viewpoint of storage stability of the pre-curable composition, it is more preferable that the SH group is a secondary thiol.

Examples of the compound having two or more SH groups include 1,2-ethane dithiol, 1,2-propane dithiol, 1,3-propane dithiol, 1,4-butane dithiol, 1,6-hexanedithiol, 6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonene dithiol, 12-dodecane dithiol, 2,2-dimethyl-1,3-propane dithiol, 3-methyl-1,5-pentane dithiol, Cyclohexanedimethanol, 1-cyclohexanedimethanol, 1-cyclohexanedimethanol, 1-cyclohexanedimethanol, 1-cyclohexanedimethanol, Bis (cyclohexane) bicyclo [2,2,1] hepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoacetate), and ethylene glycol bis (3-mercaptopropionate); 1,1,1-tris (mercaptomethyl) ethane, 2-ethyl-2-mercaptomethyl-1,3-propane dithiol, 1,2,3-propanol, Trithiol compounds such as paintless (2-mercaptoacetate), trimethylolpropanol (3-mercaptopropionate), and tris ((mercaptopropionyloxy) -ethyl) isocyanurate; Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutanate), dipentaerythritol hexa-3- And thiol compounds having 4 or more SH groups such as mercaptopropionate.

Examples of the compound having a secondary thiol include a car lens MT PE1, a car lens MT NR1, and a car lens MT BD1 (trade name, manufactured by Showa Denko K.K.).

Such SH group-containing compound (D) can be suitably selected from the group consisting of "CALENS MT PE1", "CALENS MT BD1" and "CALENS MT NR1" (all trade names) manufactured by Showa Denko have.

When the sum of the polymerizable components in the active energy ray-curable composition is 100 parts by mass, the compound (D) containing the SH group is preferably 1 to 60 parts by mass, more preferably 1 to 15 parts by mass. When the content of the SH group-containing compound (D) is 1 part by mass or more, the elastic modulus of the surface layer can be lowered while maintaining the crosslinking density, so that contamination can be easily pushed out from the recessed portion. As a result, And the restoring force of the shape of the convex portion can be maintained. When the content of the SH group-containing compound (D) is 60 parts by mass or less, the storage stability of the active energy ray curable composition can be maintained. When the content of the SH group-containing compound (D) is 15 parts by mass or less, the decrease of the elastic modulus of the surface layer can be suppressed more effectively, and the unevenness of the convex portions can be prevented.

The active energy ray-curable composition may further contain a monofunctional monomer. The monofunctional monomer is preferably selected in consideration of the compatibility with the multifunctional (meth) acrylate (A) and the silicone (meth) acrylate (C) of two or more functionalities. Examples thereof include monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group, monofunctional (meth) acrylates having a hydroxyl group in an ester group such as a hydroxyalkyl (meth) acrylate, monofunctional acrylamides, Cationic monomers such as methacrylamide propyl trimethylammonium methylsulfate or methacryloyloxyethyl trimethylammonium methylsulfate, and the like are preferably exemplified. Specific examples of mono-functional monomers include monomolecular (meth) acrylates such as "M-20G", "M-90G", and "M-230G" (all trade names available from Shin-Nakamura Chemical Co., Ltd.). In addition, from the viewpoint of improving the antifouling property, alkyl mono (meth) acrylate, silicone (meth) acrylate and alkyl fluoro (meth) acrylate are suitably used. Specific examples of such mono-functional monomers include Nemic analogue blends such as "Blemmer LA", "Blemmer CA", "Blemmer SA" (all trade names), "X-24-8201" "X-22-174DX" (all trade names), "C10GACRY" (trade name) manufactured by Exflor Research.

The active energy ray curable composition may also contain a viscosity adjuster such as acryloylmorpholine or vinyl pyrrolidone or an adhesion improver such as acryloyl isocyanate which improves the adhesion to a transparent substrate.

When the total amount of the polymerizable components in the active energy ray-curable composition is 100 parts by mass, it is preferably 0.1 to 20 parts by mass, more preferably 5 to 15 parts by mass, in the case of containing monofunctional monomers. By including the monofunctional monomer, the adhesion between the substrate and the surface layer (active energy ray curable composition) can be improved. (D) containing a polyfunctional (meth) acrylate (A), a silicone (meth) acrylate (C) and an SH group when the content of the monofunctional monomer is 20 parts by mass or less, The antifouling property can be sufficiently expressed. The monofunctional monomers may be used singly or in combination of two or more.

Further, a polymer (oligomer) having a low polymerization degree obtained by polymerizing one or more monofunctional monomers may be added to the active energy ray-curable composition. Specific examples of the polymer having such a low polymerization degree include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group (e.g., "M-230G" (trade name) manufactured by Shin Nakamura Chemical Co., Ltd.) 40/60 copolymerized oligomer of amide propyl trimethylammonium methylsulfate (e.g., "MG polymer" (trade name) manufactured by MRC Unitech Co., Ltd.).

The active energy ray curable composition may contain fine particles such as an antistatic agent, a releasing agent, an ultraviolet absorber, and colloidal silica, in addition to the various monomers and polymers having a low degree of polymerization described above.

The active energy ray curable composition may include a release agent. When the active energy ray-curable composition contains a releasing agent, good releasability can be maintained when the laminate is continuously produced. Examples of the release agent include (poly) oxyalkylene alkyl phosphoric acid compounds. Particularly, in the case of using an anodized alumina mold, the mold release agent tends to be adsorbed on the surface of the mold, because the (poly) oxyalkylene alkyl phosphate compound and alumina interact with each other.

JP-506H "(trade name) manufactured by JOHOKU CHEMICAL INDUSTRIAL CO., LTD.," MoldWiz INT-1856 "(trade name) manufactured by Axel Corporation, a product of Nikko Chemicals Co., TDP-8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP- DDP-2 "," TLP-4 "," TCP-5 ", and" DLP-10 "(all trade names).

The release agents contained in the active energy ray-curable composition may be used alone or in combination of two or more.

The content of the releasing agent contained in the active energy ray-curable composition is preferably 0.01 to 2.0 parts by mass, more preferably 0.05 to 0.2 parts by mass based on 100 parts by mass of the polymerizable component. When the content of the releasing agent is 0.01 parts by mass or more, the releasability from the mold of the article having the fine uneven structure on the surface is good. On the other hand, when the proportion of the releasing agent is 2.0 parts by mass or less, the adhesion between the cured product of the active energy ray curable composition and the base material is good, and the hardness of the cured product is adequate, whereby the fine uneven structure can be sufficiently retained.

In the laminate of the present embodiment, the elastic modulus of the surface of the micro concavo-convex structure, that is, the pressing-in modulus of elasticity of the surface layer is preferably 500 MPa or less, more preferably 50 to 100 MPa. When the surface layer has a modulus of elasticity of 50 MPa or more, the micro concavo-convex structure is sufficiently rigid so that the projections of the convex portions can be effectively prevented. When the elastic modulus of the surface layer is 500 MPa or less, the fine concavo-convex structure is soft, so that contamination entering the concave portion can be pushed out. If the elastic modulus of the surface layer is 100 MPa or less, the fine concavo-convex structure is sufficiently soft, so that the fine concavo-convex structure can be freely deformed, and contamination in the concavity can be easily removed.

In the laminate of this embodiment, the water contact angle of the surface layer of the portion where the fine uneven structure is formed is not particularly limited, but is preferably 130 deg. Or more. When the water contact angle of the surface layer is 130 DEG or more, the surface energy is sufficiently small so that the contamination can be easily wiped off. The upper limit of the water contact angle of the surface layer is not particularly limited, but is preferably 150 占 or less, and more preferably 145 占 or less.

The active energy ray curable composition of the present embodiment may suitably contain a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer. Further, the active energy ray-curable composition can be cured by a polymerization initiator described later. In addition, the active energy ray curable composition may comprise a non-reactive polymer.

Since the laminate of the present embodiment is a laminate having a surface layer having excellent antifouling properties, which can easily remove contamination, the laminate of the present embodiment can be used as an antireflective article, an image display, It is difficult to cause contamination of sebum or the like adhered at the time of use, and it is easy to fall off, and a good antireflection performance can be exhibited. In addition, since contamination can be easily removed without using water or alcohol on the surface, an article excellent in practical use can be obtained.

(Example A)

Hereinafter, the present embodiment will be described concretely by Example A, but the present invention is not limited thereto.

<Various Evaluation and Measurement Methods>

(Determination of compatibility of the curing liquid)

As evaluation of compatibility, the transparency of the active energy ray curable resin composition (state before curing) was visually observed under a fluorescent lamp.

A: transparent (good compatibility)

B: White turbidity is observed at room temperature, but when the active energy ray-curable resin composition is heated to 50 degrees, it becomes transparent.

C: cloudy white (poor compatibility) at room temperature and 50 캜

(Judgment of water contact angle)

1 [mu] l of water was dripped onto the surface of the curable resin (active energy ray curable resin) of the active energy ray curable resin composition prepared in Example A and Comparative Example A described later using an automatic contact angle measuring apparatus (manufactured by KRUSS) The contact angle of the water droplet after 7 seconds from the dropwise addition was calculated by the? / 2 method.

(Measurement of elastic modulus)

The surface of the surface layer was subjected to a load while increasing the load under the condition of 50 mN / 10 seconds using "FISCHERSCOPE (R) HM2000" (trade name, manufactured by Fisher Co.), maintained at 50 mN for 60 seconds, Reduce the load while reducing it. The elastic modulus was calculated by extrapolation using the point at which the load of 65% and 95% was applied. On the other hand, using a Teflon sheet having a thickness of 500㎛ as a spacer, an active energy ray curable resin composition sandwiched by two glass plates, the integrated light amount of irradiation light for the active energy ray curable resin composition was irradiated with ultraviolet rays with energy of 3000mJ / cm ² And then an active energy ray curable resin having a thickness of 500 mu m is prepared, and the elastic modulus of the irradiated surface (surface) of the cured resin is measured in the same manner as described above.

(Antifouling property test)

First, a simulated fingerprint liquid (manufactured by JIS K2246, manufactured by Iseki Co., Ltd.) was adhered by the method described in Japanese Patent Laid-Open No. 2006-147149 to transfer a simulated fingerprint to the surface of the laminate. In this method, approximately 1 mL is taken while the pseudo fingerprint component is well stirred with a magnetic stirrer, and this pseudo fingerprint component is coated on a polycarbonate substrate (120 mm in diameter and 1.2 mm in thickness) by spin coating Respectively. The substrate was heated at 60 占 폚 for 3 minutes to completely remove methoxypropanol as an unnecessary diluent. This was the original version of the doctor fingerprint. Continuously, NO. (12 mm in diameter) of the silicon rubber stopper of the No. 1 silicone rubber stopper was uniformly polished with # 240 abrasive paper to prepare a doctor fingerprint transferring material. The polished end face was pressed on the disk with a load of 29 N for 10 seconds The finger print component was transferred to the end face of the transfer material. Subsequently, the surface of the light-transmitting base of each sample was pressed with the load of 29 N for 10 seconds to transfer the proof paper fingerprint component. On the other hand, the fingerprint pattern was transferred to a position near a radius of 40 mm of the medium.

Subsequently, the artificial fingerprint liquid was wiped off by rubbing it six times using a professional wipe (trade name: Soft Super Wiper S132, manufactured by Daio Paper Co., Ltd.) at a pressure of 39 kPa to see whether the contamination remained in the laminate under a fluorescent lamp. Respectively. The evaluation was made based on the following criteria.

A: Pollution is not visually confirmed.

B: Some contamination is visually confirmed.

C: The doctor's fingerprints spread and the contamination is not wiped off.

(Evaluation of projection unification)

When the LED light was incident from the side of the film cross section (side) and observed in the incidence direction, it was visually observed whether white spots appeared. The evaluation was made based on the following criteria.

A: White stain is not seen when obliquely observed.

B: White stain is seen when obliquely observed, but white stain is not seen when observed from the front.

C: White stain was observed at an oblique and frontal view.

(Slope of coefficient of friction)

A friction tester (trade name: HEIDON TRIBOGEAR HHS-2000, manufactured by Shinto Scientific Co., Ltd.) was used to measure the coefficient of friction. A load of 1000 g was applied to a 2 cm square BEMCOT M-3II (trade name, manufactured by Asahi Kasei Fibers Co., Ltd.) placed on the surface of the laminate, and reciprocating abrasion was performed 50 times at a reciprocating distance of 30 mm and a head speed of 30 mm / sec. The slope of the friction coefficient was calculated from the following equation, assuming that the value of the kinetic friction coefficient at the time of first friction was μ ₁ , and the value of the kinetic friction coefficient at the 50th friction time was μ ₅₀ .

μ _s = (μ ₅₀ -μ ₁ ) / (50-1)

(Scratch resistance)

For evaluating the scratch resistance, 1000 reciprocating abrasions were carried out using the above-mentioned method. In the appearance evaluation, the light-transmitting article was attached to one side of a transparent black acrylic plate (trade name: acrylite, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 2.0 mm and evaluated visually in light of a fluorescent lamp in the room. The evaluation was made based on the following criteria.

A: The scratches are not visible to the naked eye.

B: Several scratches are visible with the naked eye.

C: Many scratches are visually confirmed.

(Observation of sample surface by electron microscope)

The fine uneven structure formed on the surface of the stamper and the laminate was observed under a condition of an acceleration voltage of 3.00 kV by using a scanning electron microscope ("JSM-7400F" manufactured by Nihon Electronics Co., Ltd.). On the other hand, regarding the observation of the laminate, observation was performed after platinum was deposited for 10 minutes. The distances between adjacent convex portions and the height of the convex portion were measured from the obtained image. The average value was obtained by measuring 10 points each.

<Fabrication of Stamper>

An electrolytically polished aluminum disc (purity 99.99 mass%, thickness 2 mm,? 65 mm) was used as the aluminum substrate. The aluminum substrate was immersed in a 0.3M oxalic acid aqueous solution adjusted to 15 DEG C and the aluminum substrate was subjected to anodic oxidation by intermittently supplying current to the aluminum substrate by repeating power ON / OFF of the DC stabilization device. Next, an operation of applying a constant voltage of 80 V for 5 seconds at intervals of 30 seconds was repeated 60 times to form an oxide film having pores. Subsequently, the aluminum substrate on which the oxide film was formed was immersed in an aqueous solution at 70 캜 mixed with 6 mass% phosphoric acid and 1.8 mass% chromium acid for 6 hours to dissolve and remove the oxide film. The aluminum substrate, from which the oxide film was dissolved and removed, was immersed in an oxalic acid aqueous solution of 0.05M adjusted to 16 占 폚 and subjected to anodic oxidation at 80 V for 7 seconds. Subsequently, the aluminum base was immersed in a 5 mass% aqueous phosphoric acid solution adjusted to 32 占 폚 for 20 minutes to enlarge the pore diameter of the oxide film. Thus, the anodic oxidation treatment and the hole diameter enlarging treatment were alternately repeated. The anodizing treatment and the hole diameter enlarging treatment were performed five times each. The obtained stamper was immersed in a 0.1 mass% aqueous solution of TDP-8 (manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, and then pulled up and dried overnight to perform mold release treatment.

The surface of the obtained porous alumina was observed with an electron microscope. As a result, a micro concavo-convex structure consisting of a substantially conical tapered concave portion having a distance of 180 nm and a depth of 180 nm between adjacent concave portions was formed.

[Example A1]

&Lt; Preparation of laminate >

The following materials were mixed to prepare an active energy ray curable resin composition.

40 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate ("Kayadard DPEA-12", number of ethylene oxide structural units in one molecule n = 12, manufactured by Nippon Kayaku Co., Ltd.)

60 parts by mass ARONIX M-260 (trade name, manufactured by TOAGOSEI Co., Ltd., average repeating unit of polyethylene glycol chain: 13)

1 part by mass Irgacure 184 (trade name, manufactured by Chiba Specialty Chemicals)

0.5 part (trade name, product name, manufactured by Chiba Specialty Chemicals)

0.1 part by mass of TDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd.)

A few drops of the active energy ray-curable resin composition were dropped on the stamper, and the stamper was coated while stretching by pressing with a triacetyl cellulose film (FTTD80ULM (trade name), manufactured by Fuji Film). Subsequently, the active energy ray curable resin composition was photo-cured by irradiating ultraviolet rays at an energy of 1000 mJ / cm ² at a film side. Thereafter, the film and the stamper were peeled off to obtain a laminate having a fine concavo-convex structure as shown in Fig. 1, in which the distance w1 between neighboring convex portions was 180 nm and the height d1 of the convex portion was 180 nm.

<Evaluation>

The water contact angle, elastic modulus, antifouling property, slope (μ _s ) of the coefficient of friction, antiscratching property, and projected unity of the obtained laminate were evaluated for compatibility in the active energy ray curable resin composition. The results are shown in Table 2.

The abbreviations in Table 1 are as follows.

DPHA: dipentaerythritol hexaacrylate ("KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.)

DPEA-12: ethylene oxide-modified dipentaerythritol hexaacrylate ("KAYARAD DPEA-12" manufactured by Nippon Kayaku Co., Ltd., n = 12 ethylene oxide structural units in one molecule)

DPEA-18 (trade name &quot; DPHA-18EO denatured &quot;, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., number of ethylene oxide structural units in one molecule n = 18)

M-260: Polyethylene glycol diacrylate ("Aronix M-260" manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13)

APG-700: polypropylene glycol diacrylate (average repeating unit of polypropylene glycol chain, manufactured by Shin-Nakamura Chemical Co., Ltd. is 12)

BYK-UV3570: Silicone acrylate Propylene oxide-modified neopentyl glycol diacrylate Diluted product (manufactured by Big Chem Japan)

PE1: car lens MT PE1 (trade name, a compound having four SH groups, manufactured by Showa Denko Co., Ltd.)

IRG. 184: Hydroxycyclohexyl phenyl ketone (&quot; Irgacure 184 &quot;, manufactured by Chiba Specialty Chemicals)

IRG. 819: phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide ("Ilgacure 819", manufactured by Chiba Specialty Chemicals)

TDP-2: polyoxyethylene alkylether phosphoric acid (trade name, manufactured by Nikko Chemicals Co., Ltd.)

[Examples A2 to A19]

A laminate was obtained in the same manner as in Example A1 except that the active energy ray-curable resin composition having the composition shown in Table 1 was used. The results are shown in Table 2.

[Example A20]

A laminate having a cured layer was obtained in the same manner as in Example A1 except that the active energy ray-curable resin composition having the composition shown in Table 1 was used. PC-3B (trade name, manufactured by Fluoro Technologies) was applied as a primer to the cured layer having the fine uneven structure obtained by spin coating. Thereafter, after drying at room temperature for 90 minutes, FG5070S135-0.1 (trade name, manufactured by Floro Technologies) was spin-coated and dried at 60 DEG C for 3 hours to obtain a laminate having a surface-treated layer. The results are shown in Table 2.

[Comparative Examples A1 to A3]

A laminate was obtained in the same manner as in Example A1 except that the active energy ray-curable resin composition having the composition shown in Table 1 was used. The results are shown in Table 2.

In the laminates obtained in Examples A1 to A20, the elastic modulus of the surface layer was less than 250 MPa and the slope of the coefficient of friction was 1.8 x 10 &lt; ^-3 &gt; or less. Thus, the antifouling property and the excellent scratch resistance .

The laminate obtained in Examples A11 to A13 and A19, in which the elastic modulus of the surface layer was 45 to 65 MPa and the water contact angle of the surface layer was 135 or more, was particularly excellent in compatibility and antifouling property.

Particularly, in the layered product obtained in Examples A12 and A20, in which the elastic modulus of the surface layer was 50 to 65 MPa and the surface contact angle of water was 140 占 or more, a laminate having excellent compatibility, antifouling property and scratch resistance was obtained.

The antifouling properties of the laminates obtained in Comparative Examples A1 to A3 were not sufficient.

In Comparative Example A3, since the scratch resistance was inferior, a number of scratches occurred in the surface layer during the evaluation and the surface layer was broken and peeled off, so evaluation was stopped.

(Example B)

Hereinafter, the present embodiment will be described concretely by Example B, but the present invention is not limited thereto.

<Various Evaluation and Measurement Methods>

(Measurement of water contact angle)

1 [mu] l of water was added dropwise to the surface of the surface layer of the laminate produced in Example B and Comparative Example B described later using an automatic contact angle measuring apparatus (manufactured by KRUSS). The contact angle after 7 seconds was calculated by the? / 2 method.

(Measurement of elastic modulus)

Using a Teflon sheet having a thickness of 500 탆 as a spacer, the active energy ray curable resin composition was sandwiched between two glass plates and irradiated with ultraviolet rays at an energy of 3000 mJ / cm ² . Thus, the active energy ray-curable resin composition was photo-cured to produce a cured product of an active energy ray-curable resin composition having a thickness of 500 mu m. The irradiated surface of the cured product was loaded for 60 seconds under the condition of 50 mN / 10 seconds using "FISCHERSCOPE (R) HM2000" (trade name, manufactured by Fisher) and then removed under the same conditions as the load. The modulus of elasticity was calculated by extrapolation using the point at which 65% and 95% load was applied.

(Antifouling property test)

Artificial fingerprint liquid (manufactured by JIS K2246 ISEKI Co., Ltd.) was adhered by the method described in JP-A-2006-147149, and the doctor fingerprints were transferred to the surface of the laminate. Specifically, about 1 mL of the false fingerprint component was sampled while being well stirred with a magnetic stirrer, and then coated on a polycarbonate substrate (diameter 120 mm, thickness 1.2 mm) by spin coating. The substrate was heated at 60 占 폚 for 3 minutes to completely remove methoxypropanol as an unnecessary diluent. This was the original version of the doctor fingerprint. Continuously, NO. (12 mm in diameter) of the silicon rubber stopper of the No. 1 silicone rubber stopper was uniformly polished with # 240 abrasive paper to prepare a doctor fingerprint transferring material. The polished end face was pressed on the disk with a load of 29 N for 10 seconds The finger print component was transferred to the end face of the transfer material. Subsequently, the surface of the translucent base of each of the samples was pressed with the load of 29 N for 10 seconds to transfer the proof paper fingerprint component. On the other hand, the fingerprint pattern was transferred to a position near a radius of 40 mm of the medium. Next, the artificial fingerprint liquid was wiped off by using a professional wipe (trade name: Soft Super Wiper S132, manufactured by Daio Paper Co., Ltd.) at a pressure of 98 kPa for 6 round trips, and then, Observed with the naked eye. The evaluation was made based on the following criteria.

○: The contamination is not visually confirmed.

X: The doctor fingerprint spreads, and the pollution does not wipe out.

(Observation of sample surface by electron microscope)

Microstructure of the surface unevenness formed on the surface of the surface layer of the stamper and the laminate was observed under a condition of an acceleration voltage of 3.00 kv by using a scanning electron microscope (trade name: "JSM-7400F", manufactured by Nihon Electronics Co., Ltd.). On the other hand, regarding the observation of the surface layer of the laminate, observation was performed after platinum was deposited for 10 minutes. The distances between adjacent convex portions and the height of the convex portion were measured from the obtained image.

(Evaluation of projection unification)

When the LED light was incident from the film cross-section side (side face side) of the laminate and observed in the incident direction, whether or not white speckle was observed was visually observed. The evaluation was made based on the following criteria.

○: White stain is not seen when obliquely observed.

B: White stain was not observed when observed from the front.

X: White stain is observed when observed from the front.

<Fabrication of Stamper>

An aluminum master plate having a purity of 99.99% by mass, electrolytically polished and having a thickness of 2 mm and a diameter of 65 mm was used as an aluminum substrate. The aqueous solution of 0.3 M oxalic acid was adjusted to 15 캜, the aluminum substrate was immersed, and the power supply of the DC stabilization device was repeatedly turned on and off. As a result, an electric current was intermittently supplied to the aluminum substrate to perform anodic oxidation. An operation of applying a constant voltage of 80 V for 5 seconds at intervals of 30 seconds was repeated 60 times to form an oxide film having pores. Subsequently, the aluminum substrate on which the oxide film was formed was immersed in an aqueous solution of 70 ° C mixed with 6 mass% phosphoric acid and 1.8 mass% chromium acid for 6 hours to dissolve and remove the oxide film. The aluminum substrate from which the oxide film was dissolved and dissolved was immersed in an oxalic acid aqueous solution of 0.05M adjusted to 16 占 폚 and subjected to anodic oxidation at 80 V for 7 seconds. Subsequently, this was immersed in a 5 mass% aqueous phosphoric acid solution adjusted to 32 DEG C for 20 minutes to carry out enlargement of the pore diameter to enlarge the pores of the oxide film. Thus, the anodic oxidation and the hole diameter enlarging process were alternately repeated, and the process was repeated five times in total. The resulting stamper was immersed in a 0.1 mass% aqueous solution of TDP-8 (trade name, manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, and then pulled up and air-dried overnight.

Observation of the surface of the obtained stamper by an electron microscope revealed that a micro concavo-convex structure formed of a substantially conical tapered concave portion having an interval of 180 nm and a depth of 180 nm between adjacent concave portions was formed.

[Example B1]

&Lt; Preparation of laminate >

40 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate (trade name: Kayadard DPEA-12, manufactured by Nippon Kayaku Co., Ltd., the number of ethylene oxide structural units in one molecule n = 12), ARONIX M- , The average repeating unit of ethylene glycol (13), 60 parts by mass) was used as the polymerizable component. 1 part by mass of Irgacure 184 (trade name, manufactured by BASF), 0.5 parts by mass of Irgacure 819 (trade name, manufactured by BASF) and 0.1 part by mass of TDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd.) were dissolved in the polymerizable component . Thus, an active energy ray curable resin composition was obtained. A few drops of the active energy ray-curable resin composition were dropped on the stamper, and the film was stretched by pressing with a triacetyl cellulose film (trade name: FTTD80ULM, manufactured by Fuji Photo Film Co., Ltd., hereinafter also referred to as a film) The resin composition was coated. Thereafter, ultraviolet rays were irradiated at an energy of 1000 mJ / cm ^{2 on} the film side to photo-cure the active energy ray curable resin composition. The stamper was peeled off from the cured product of the active energy ray curable resin composition to form a micro concavo-convex structure having a 180 nm interval between adjacent convex portions and a height d1 of convex portion as shown in Fig. 1 on the surface of the surface layer 12 (10) was obtained.

<Evaluation>

Evaluation of water contact angle, elastic modulus, antifouling property and projected unity were carried out on the basis of the various evaluation and measurement methods described above. The results are shown in Table 3.

[Examples B2 to B6, Comparative Examples B1 to B3]

A laminate was prepared in the same manner as in Example B1, except that the kind of the polymerization initiator, the kind of the polymerization initiator, and the blending amount were changed as shown in Table 1 in the preparation of the active energy ray curable resin composition. The results are shown in Table 3.

The abbreviations in Table 3 are as follows.

DPHA: Dipentaerythritol hexaacrylate (trade name: Kayadard DPHA, manufactured by Nippon Kayaku Co., Ltd.)

DPEA-12: ethylene oxide-modified dipentaerythritol hexaacrylate (trade name: Kayadard DPEA-12, manufactured by Nippon Kayaku Co., Ltd., n = 12 ethylene oxide structural units in one molecule)

DPEA-18: ethylene oxide-modified dipentaerythritol hexaacrylate (trade name: DPEA-18, manufactured by Daiichi Kogyo K.K., the number of ethylene oxide structural units in one molecule n = 18)

M-260: Polyethylene glycol diacrylate (manufactured by TOA Corporation, average repeating unit of ethylene glycol: 13)

APG700: polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., the average repeating unit of propylene glycol is 12)

IRG. 184: IRGACURE 184 (trade name, hydroxycyclohexyl phenyl ketone manufactured by BASF)

IRG. 819: IRGACURE 819 (trade name, phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide manufactured by BASF)

TDP-2: TDP-2 (trade name, polyoxyethylene alkylether phosphoric acid, manufactured by Nikko Chemicals Co., Ltd.).

On the other hand, in Table 3, Examples 1 to 6 and Comparative Examples 1 to 3 show Examples B1 to B6 and Comparative Examples B1 to B3, respectively.

In Examples B1 to B6, since the elastic modulus was less than 200 MPa, the antifouling property was excellent, and the contamination could be easily removed without using water or alcohol. Particularly, in Examples B1, B2 and B5, since the modulus of elasticity was in the range of 90 to 150 MPa, the projections of the fine concavo-convex structure were not projected, and the antifouling property was excellent.

On the other hand, in Comparative Examples B1 and B2, since the elastic modulus was 200 MPa or more, the antifouling property was insufficient, and the contamination could not be easily removed without using water or alcohol. Further, in Comparative Example B3, polypropylene glycol diacrylate was used instead of polyethylene glycol diacrylate, so that the mobility of the molecule was low and the stain resistance was insufficient, so that the contamination could be easily removed without using water or alcohol There was no.

(Example C)

Hereinafter, the present embodiment will be described concretely by Example C, but the present invention is not limited thereto.

<Various Evaluation and Measurement Methods>

(Determination of compatibility of the curing liquid)

As evaluation of compatibility, the transparency of the active energy ray curable resin composition (state before curing) was visually observed under a fluorescent lamp.

○: Transparent (good compatibility)

?: Although opaque at room temperature, when the active energy ray-curable resin composition is heated to 50 degrees, it becomes transparent.

X: cloudy white (poor compatibility) at room temperature and 50 deg.

(Judgment of water contact angle)

Water was added dropwise to the surface of a cured resin (active energy ray curable resin) of the active energy ray-curable resin composition prepared in Example C and Comparative Example C described later by using 1 l of water using an automatic contact angle measuring apparatus (manufactured by KRUSS) , And the contact angle of the water droplet after 7 seconds from the dropwise addition was calculated by the? / 2 method.

(Measurement of elastic modulus)

The surface of the surface layer was subjected to a load while increasing the load under the condition of 50 mN / 10 seconds by using "FISCHERSCOPE (R) HM2000" (trade name, manufactured by Fisher), maintained at 50 mN for 60 seconds, To reduce the load while reducing the load. The elastic modulus was calculated by extrapolation using the point at which the load of 65% and 95% was applied. On the other hand, using a Teflon sheet having a thickness of 500㎛ as a spacer, an active energy ray curable composition sheathed in two glass plates, the integrated light dose 3000mJ / cm was irradiated with ultraviolet rays with energy of the ^second photo-curing the active energy ray curable resin composition , An active energy ray curable resin having a thickness of 500 mu m may be prepared and the elastic modulus may be calculated on the irradiation surface of the cured resin in the same manner as described above.

(Antifouling property test)

The method described in Japanese Patent Application Laid-Open No. 2006-147149 (the false fingerprint component was applied by spin coating onto a polycarbonate substrate (diameter: 120 mm, thickness: 1.2 mm) while collecting about 1 mL while being well stirred with a magnetic stirrer . This substrate was heated at 60 DEG C for 3 minutes to completely remove methoxypropanol, which is an unnecessary diluent. This was used as a disk for the doctor fingerprint transfer. The cross section (diameter 12 mm) was uniformly polished with # 240 abrasive paper, and the polished cross section was pressed against the original plate with a load of 29 N for 10 seconds to transfer the false fingerprint component to the end face of the transfer material . Subsequently, the surface of the transparent substrate of each sample was pressed with the load of 29 N for 10 seconds to transfer the proof fingerprint components. [0100] On the other hand, (JIS K2246 manufactured by Iseki Co., Ltd.) was adhered to the surface of the layered body to transfer the doctor fingerprints to the surface of the layered body. Next, the artificial fingerprint liquid was wiped off by using a professional wipe (trade name: Soft Super Wiper S132, manufactured by Daio Paper Co., Ltd.) at a pressure of 98 kPa for 6 round trips, and then, Observed with the naked eye. The evaluation was made based on the following criteria.

◎: Pollution is not visually confirmed.

?: A slight contamination was visually confirmed.

X: The doctor fingerprint spreads, and the pollution does not wipe out.

(Evaluation of projection unification)

When the LED light was incident from the side of the film cross section (side) and observed in the incidence direction, it was visually observed whether white spots appeared. The evaluation was made based on the following criteria.

○: White stain is not seen when obliquely observed.

?: White stain is seen when obliquely observed, but white stain is not seen when observed from the front.

X: White stain is seen at an oblique angle and when viewed from the front.

(Observation of sample surface by electron microscope)

The fine uneven structure formed on the surface of the stamper and the laminate was observed under a condition of an acceleration voltage of 3.00 kV by using a scanning electron microscope ("JSM-7400F" manufactured by Nihon Electronics Co., Ltd.). On the other hand, regarding the observation of the laminate, observation was performed after platinum was deposited for 10 minutes. The distances between adjacent convex portions and the height of the convex portion were measured from the obtained image. The average value was obtained by measuring 10 points each.

<Fabrication of Stamper>

An electrolytically polished aluminum disc (purity 99.99 mass%, thickness 2 mm,? 65 mm) was used as the aluminum substrate. The aluminum substrate was immersed in an aqueous 0.3M oxalic acid solution adjusted to 15 DEG C and the aluminum substrate was subjected to anodic oxidation by intermittently supplying current to the aluminum substrate by repeating power ON / OFF of the DC stabilization device. Next, an operation of applying a constant voltage of 80 V for 5 seconds at intervals of 30 seconds was repeated 60 times to form an oxide film having pores. Subsequently, the aluminum substrate on which the oxide film was formed was immersed in an aqueous solution at 70 캜 mixed with 6 mass% phosphoric acid and 1.8 mass% chromium acid for 6 hours to dissolve and remove the oxide film. The aluminum substrate, from which the oxide film was dissolved and removed, was immersed in an oxalic acid aqueous solution of 0.05M adjusted to 16 占 폚 and subjected to anodic oxidation at 80 V for 7 seconds. Subsequently, the aluminum base was immersed in a 5 mass% aqueous phosphoric acid solution adjusted to 32 占 폚 for 20 minutes to enlarge the pore diameter of the oxide film. Thus, the anodic oxidation treatment and the hole diameter enlarging treatment were alternately repeated. The anodizing treatment and the hole diameter enlarging treatment were performed five times each. The obtained stamper was immersed in a 0.1 mass% aqueous solution of TDP-8 (manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, and then pulled up and dried overnight to perform mold release treatment.

The surface of the obtained porous alumina was observed with an electron microscope. As a result, a micro concavo-convex structure consisting of a substantially conical tapered concave portion having a distance of 180 nm and a depth of 180 nm between adjacent concave portions was formed.

[Example C1]

&Lt; Preparation of laminate >

The following materials were mixed to prepare an active energy ray curable resin composition.

27 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate ("Kayadrad DPEA-12", number of ethylene oxide structural units in one molecule n = 12, manufactured by Nippon Kayaku Co., Ltd.)

Aronix M-260 (trade name, manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13) 64 parts by mass

9 parts by mass of BYK-3570 (trade name, manufactured by Big Chem Japan, tetrafunctional silicone acrylate / propylene oxide-modified neopentyl glycol diacrylate = 7/3)

1 part by mass Irgacure 184 (trade name, manufactured by Chiba Specialty Chemicals)

0.5 part (trade name, product name, manufactured by Chiba Specialty Chemicals)

0.1 part by mass of TDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd.)

A few drops of the active energy ray-curable resin composition were dropped on the stamper and covered with a triacetyl cellulose film (FTTD80ULM (trade name), manufactured by Fuji Film) while spreading. Subsequently, the active energy ray curable resin composition was photo-cured by irradiating ultraviolet rays at an energy of 1000 mJ / cm ² at a film side. Thereafter, the film and the stamper were peeled off to obtain a laminate having a fine concavo-convex structure as shown in Fig. 1, in which the distance w1 between neighboring convex portions was 180 nm and the height d1 of the convex portion was 180 nm.

<Evaluation>

The compatibility of the components in the active energy ray-curable resin composition and the evaluation of the water contact angle, elastic modulus, antifouling property and unity of the projections of the obtained laminate were evaluated. The results are shown in Table 4.

The abbreviations in Table 4 are as follows.

DPEA-12: ethylene oxide-modified dipentaerythritol hexaacrylate ("KAYARAD DPEA-12" manufactured by Nippon Kayaku Co., Ltd., n = 12 ethylene oxide structural units in one molecule)

M-260: Polyethylene glycol diacrylate ("Aronix M-260" manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13)

APG-700: polypropylene glycol diacrylate (average repeating unit of polypropylene glycol chain, manufactured by Shin-Nakamura Chemical Co., Ltd. is 12)

BYK-3570: Silicone acrylate Propylene oxide-modified neopentyl glycol diacrylate Diluted product (manufactured by Big Chem Japan)

IRG. 184: Hydroxycyclohexyl phenyl ketone (&quot; Irgacure 184 &quot;, manufactured by Chiba Specialty Chemicals)

IRG. 819: phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide ("Ilgacure 819", manufactured by Chiba Specialty Chemicals)

TDP-2: polyoxyethylene alkylether phosphoric acid (trade name, manufactured by Nikko Chemicals Co., Ltd.)

On the other hand, in Table 4, Examples 1 to 8 and Comparative Example 1 show Examples C1 to C8 and Comparative Example C1, respectively.

[Examples C2 to C8]

A laminate was obtained in the same manner as in Example C1 except that the composition shown in Table 4 was used. The results are shown in Table 4.

[Comparative Example C1]

A laminate was obtained in the same manner as in Example C1 except that the composition shown in Table 4 was used. The results are shown in Table 4.

In the laminates obtained in Examples C1 to C8, the water contact angle of the surface layer was 130 deg. Or more, and the stain-proofing property was obtained which can easily remove contamination without using water or alcohol. In the layered product obtained in Examples C5 to C7, since silicone acrylate was not less than 45 parts by mass, excellent antifouling properties were exhibited. Further, in the layered product obtained in Examples C5 and C6, since the amount of silicon acrylate is 45 to 65 parts by mass, the compatibility of the active energy ray-curable resin composition is good, the projections are united and the excellent antifouling property Respectively.

The antifouling property of the laminate obtained in Comparative Example C1 was not sufficient.

(Example D)

Hereinafter, the present embodiment will be described concretely by Example D, but the present invention is not limited thereto.

<Various Evaluation and Measurement Methods>

(Judgment of water contact angle)

Water was dropped onto the surface of the laminate prepared in Example D and Comparative Example D described below by using 1 l of water using an automatic contact angle measuring apparatus (manufactured by KRUSS), and the contact angle of the water droplet after 7 seconds after the drop was & 2 method.

(Measurement of elastic modulus)

A sheet coated with Teflon (registered trademark) having a thickness of 500 탆 was used as a spacer, the active energy ray curable composition was sandwiched between two glass plates, and ultraviolet rays were irradiated at an energy of 3000 mJ / cm ^{2 to} prepare an active energy ray curable resin composition Curing resin to prepare an active energy ray curable resin having a thickness of 500 mu m and coating the surface treatment layer on the irradiation surface side to obtain a laminate. The surface treated layer side of the laminate thus prepared was subjected to a load while increasing the load under the condition of 50 mN / 10 seconds by using a FischerCOPE (R) HM2000 manufactured by Fisher Co., holding it at 50 mN for 60 seconds, While reducing the load. The elastic modulus (indentation elastic modulus) of the cured resin was calculated by extrapolation using the point at which the load of 65% and 95% was applied. On the other hand, the active energy is irradiated with ultraviolet rays to a sheet coated with Teflon (registered trademark) having a thickness of 500㎛ by using as a spacer, sheathed with an active energy beam curable composition of the two glass plates, the integrated light amount of irradiation energy of 3000mJ / cm ² The radiation curable resin composition may be photocured to prepare an active energy ray curable resin having a thickness of 500 mu m and the elastic modulus may be calculated by measuring the irradiation surface of the cured resin in the same manner as described above.

(Antifouling property test)

The method described in Japanese Patent Application Laid-Open No. 2006-147149 (the false fingerprint component was applied by spin coating onto a polycarbonate substrate (diameter: 120 mm, thickness: 1.2 mm) while collecting about 1 mL while being well stirred with a magnetic stirrer . This substrate was heated at 60 DEG C for 3 minutes to completely remove methoxypropanol, which is an unnecessary diluent. This was used as a disk for the doctor fingerprint transfer. The cross section (diameter 12 mm) was uniformly polished with # 240 abrasive paper, and the polished cross section was pressed against the original plate with a load of 29 N for 10 seconds to transfer the false fingerprint component to the end face of the transfer material . Subsequently, the surface of the transparent substrate of each sample was pressed with the load of 29 N for 10 seconds to transfer the proof fingerprint components. [0100] On the other hand, (JIS K2246 manufactured by Iseki Co., Ltd.) was adhered to the surface of the layered body to transfer the doctor fingerprints to the surface of the layered body. Next, the artificial fingerprint liquid was wiped off by wiping six rounds at a pressure of 98 kPa using a professional wipe (trade name: Soft Super Wiper S132, manufactured by Daio Paper Co., Ltd.), and visually observed for stains remaining in the laminate under a fluorescent lamp did. The evaluation was made based on the following criteria.

◎: Pollution is not visually confirmed.

?: A slight contamination was visually confirmed.

X: The doctor fingerprint spreads, and the pollution does not wipe out.

(Observation of the surface of the laminate by electron microscope)

The fine uneven structure formed on the surface of the stamper and the laminate was observed under a condition of an acceleration voltage of 3.00 kV by using a scanning electron microscope ("JSM-7400F" manufactured by Nihon Electronics Co., Ltd.). On the other hand, regarding the observation of the laminate, observation was performed after platinum was deposited for 10 minutes. The distances between adjacent convex portions and the height of the convex portion were measured from the obtained image. The average value was obtained by measuring 10 points each.

<Fabrication of Stamper>

An electrolytically polished aluminum disc (purity 99.99 mass%, thickness 2 mm,? 65 mm) was used as the aluminum substrate. The aluminum substrate was immersed in an aqueous 0.3M oxalic acid solution adjusted to 15 DEG C and the aluminum substrate was subjected to anodic oxidation by intermittently supplying current to the aluminum substrate by repeating power ON / OFF of the DC stabilization device. Next, an operation of applying a constant voltage of 80 V for 5 seconds at intervals of 30 seconds was repeated 60 times to form an oxide film having pores. Subsequently, the aluminum substrate on which the oxide film was formed was immersed in an aqueous solution at 70 캜 mixed with 6 mass% phosphoric acid and 1.8 mass% chromium acid for 6 hours to dissolve and remove the oxide film. The aluminum substrate, from which the oxide film was dissolved and removed, was immersed in an oxalic acid aqueous solution of 0.05M adjusted to 16 占 폚 and subjected to anodic oxidation at 80 V for 7 seconds. Subsequently, the aluminum base was immersed in a 5 mass% aqueous phosphoric acid solution adjusted to 32 占 폚 for 20 minutes to enlarge the pore diameter of the oxide film. Thus, the anodic oxidation treatment and the hole diameter enlarging treatment were alternately repeated. The anodizing treatment and the hole diameter enlarging treatment were performed five times each. The resulting stamper was immersed in a 0.1 mass% aqueous solution of TDP-8 (manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, then pulled up and dried overnight to perform mold release treatment.

The surface of the obtained porous alumina was observed with an electron microscope. As a result, a micro concavo-convex structure consisting of a substantially conical tapered concave portion having a distance of 180 nm and a depth of 180 nm between adjacent concave portions was formed.

[Example D1]

&Lt; Preparation of laminate >

The following materials were mixed to prepare an active energy ray curable resin composition.

30 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate ("Kayadrad DPEA-12", number of ethylene oxide structural units in one molecule n = 12, manufactured by Nippon Kayaku Co., Ltd.)

70 parts by mass of Aronix M-260 (trade name, manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13)

1 part by mass Irgacure 184 (trade name, manufactured by Chiba Specialty Chemicals)

0.5 part (trade name, product name, manufactured by Chiba Specialty Chemicals)

0.1 part by mass of TDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd.)

A few drops of the active energy ray-curable resin composition were dropped on the stamper and covered with a triacetyl cellulose film (FTTD80ULM (trade name), manufactured by Fuji Film) while spreading. Subsequently, ultraviolet rays were irradiated at an energy of 1000 mJ / cm ² from the film side to photo-cure the active energy ray curable resin composition. Thereafter, the film and the stamper were peeled off, and PC-3B (trade name, manufactured by Fluoro Technology Co., Ltd.) was applied as a primer to the surface layer having the fine concavo-convex structure obtained by brushing the surface of the micro concavo-convex structure with 벰 Coat M-3II (manufactured by Asahi Kasei Fiber Co., Ltd.) And dried at room temperature for 90 minutes. Then, FG5070S135-0.1 (trade name, manufactured by Floro Technologies) was coated with a brush and dried at 60 DEG C for 3 hours. Subsequently, ultraviolet rays were irradiated from the film side at an energy of 1000 mJ / cm ² in total light irradiation to photo-cure the active energy ray-curable resin composition to form a surface treatment layer. Thereafter, the film and the stamper were peeled off to obtain a laminate having a fine concavo-convex structure as shown in Fig. 3, in which the distance w1 between adjacent convex portions was 180 nm and the height d1 of the convex portion was 180 nm.

<Evaluation>

The water contact angle, elastic modulus and antifouling property of the obtained laminate were evaluated. The results are shown in Table 4.

The abbreviations in Table 5 are as follows.

DPEA-12: ethylene oxide-modified dipentaerythritol hexaacrylate ("KAYARAD DPEA-12" manufactured by Nippon Kayaku Co., Ltd., n = 12 ethylene oxide structural units in one molecule)

BYK-3570: Silicone acrylate Propylene oxide-modified neopentyl glycol diacrylate Diluted product (manufactured by Big Chem Japan)

TAS: a mixture obtained by condensation reaction of trimethylolethane / acrylic acid / succinic anhydride to 2/4/1 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

M-260: Polyethylene glycol diacrylate ("Aronix M-260" manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13)

X-22-1602: Silicone acrylate (manufactured by Shin-Etsu Chemical Co., Ltd.)

C6DA: 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

IRG. 184: Hydroxycyclohexyl phenyl ketone (&quot; Irgacure 184 &quot;, manufactured by Chiba Specialty Chemicals)

IRG. 819: phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide ("Ilgacure 819", manufactured by Chiba Specialty Chemicals)

TDP-2: polyoxyethylene alkylether phosphoric acid (trade name, manufactured by Nikko Chemicals Co., Ltd.)

PC-3B: Primer (trade name, manufactured by Floro Technologies)

FG5070S135: Fluorine coating agent (trade name, manufactured by Floro Technologies)

On the other hand, in Table 5, Examples 1 to 2 and Comparative Examples 1 and 2 show Examples D1 to D2 and Comparative Examples D1 to D2, respectively.

[Example D2]

A layered product was obtained in the same manner as in Example D1 except that the composition shown in Table 5 was used. The results are shown in Table 5.

[Comparative Examples D1 to D2]

A layered product was obtained in the same manner as in Example D1 except that the composition shown in Table 5 was used. The results are shown in Table 5.

In the laminates obtained in Examples D1 to D2, the water contact angle of the surface layer was 120 deg. Or more, and the stain-proofing property was obtained, which can easily remove contamination even without using water or alcohol. In the laminate obtained in Example D2, the elastic modulus was 100 MPa or less and the water contact angle was 130 DEG or more.

The antifouling properties of the laminate obtained in Comparative Examples D1 to D2 were not sufficient.

(Example E)

Hereinafter, the present embodiment will be described concretely by Example E, but the present invention is not limited thereto.

<Various Evaluation and Measurement Methods>

(Judgment of water contact angle)

1 [mu] l of water was dropped onto the surface of the cured product (active energy ray curable resin) of the active energy ray curable composition prepared in Example E and Comparative Example E described later using an automatic contact angle measuring apparatus (manufactured by KRUSS) , And the contact angle of the water droplet after 7 seconds was calculated by the? / 2 method.

(Measurement of indentation elastic modulus)

The surface to be irradiated on the surface layer of the laminate was subjected to a load while increasing the load under the condition of 100 mN / 10 seconds using "FISCHERSCOPE (R) HM2000" (trade name, manufactured by Fisher Co.), maintained at 100 mN for 60 seconds, The load is reduced under the condition of 10 seconds. The elastic modulus was calculated by extrapolation using the point at which the load of 65% and 95% was applied. On the other hand, using a Teflon sheet having a thickness of 500㎛ as a spacer, sheathed with an active energy beam curable composition of the two glass plates, irradiated with ultraviolet rays with energy of the integrated light dose 3000mJ / cm ² by light curing the active energy ray-curable composition , An active energy ray curable resin having a thickness of 500 mu m is prepared and the elastic modulus can be calculated by measuring the irradiation surface of the cured resin in the same manner as described above.

(Antifouling property test)

An antifouling property test was carried out according to the method described in Japanese Patent Application Laid-Open No. 2006-147149. First, about 1 mL of the false fingerprint component was sampled while being well stirred with a magnetic stirrer, and applied on a polycarbonate substrate (diameter 120 mm, thickness 1.2 mm) by spin coating. The substrate was heated at 60 占 폚 for 3 minutes to completely remove methoxypropanol as an unnecessary diluent. This was the original version of the doctor fingerprint.

Subsequently, (12 mm in diameter) of the silicon rubber stopper of the No. 1 silicone rubber stopper was uniformly polished with # 240 abrasive paper to prepare a doctor fingerprint transferring material. The polished end face was pressed on the disk with a load of 29 N for 10 seconds The finger print component was transferred to the end face of the transfer material. Subsequently, the surface of the layered product of each sample was pressed with the load of 29 N for 10 seconds so as to transfer the doctor fingerprint components. On the other hand, the fingerprint pattern was transferred to a position near a radius of 40 mm of the medium.

Next, the doctor fingerprints were wiped off six times by using a professional wipe (trade name: Soft Super Wiper S132, manufactured by Daio Paper Co., Ltd.) at a pressure of 98 kPa to visually observe the presence of contamination on the laminate under a fluorescent lamp did. The evaluation was made based on the following criteria.

◎: Pollution is not visually confirmed.

?: A slight contamination was visually confirmed.

X: The doctor fingerprint spreads, and the pollution does not wipe out.

(Evaluation of projection unification)

When the LED light was incident on the film cross-section side (side surface) and observed in the incidence direction, it was visually observed whether white speckle was seen. The evaluation was made based on the following criteria.

○: White stain is not seen when obliquely observed.

?: White stain is seen when obliquely observed, but white stain is not seen when observed from the front.

X: White stain is seen at an oblique angle and when viewed from the front.

(Observation of sample surface by electron microscope)

The fine uneven structure formed on the surface of the stamper and the laminate was observed under a condition of an acceleration voltage of 3.00 kV by using a scanning electron microscope ("JSM-7400F" manufactured by Nihon Electronics Co., Ltd.). On the other hand, regarding the observation of the laminate, observation was performed after platinum was deposited for 10 minutes. The distances between adjacent convex portions and the height of the convex portion were measured from the obtained image. The average value was obtained by measuring 10 points each.

<Fabrication of Stamper>

An electrolytically polished aluminum disc (purity 99.99 mass%, thickness 2 mm,? 65 mm) was used as the aluminum substrate. The aluminum substrate was immersed in an aqueous 0.3M oxalic acid solution adjusted to 15 DEG C and the aluminum substrate was subjected to anodic oxidation by intermittently supplying current to the aluminum substrate by repeating power ON / OFF of the DC stabilization device. Next, an operation of applying a constant voltage of 80 V for 5 seconds at intervals of 30 seconds was repeated 60 times to form an oxide film having pores. Subsequently, the aluminum substrate on which the oxide film was formed was immersed in an aqueous solution at 70 캜 mixed with 6 mass% phosphoric acid and 1.8 mass% chromium acid for 6 hours to dissolve and remove the oxide film. The aluminum substrate on which the oxide film was dissolved and removed was immersed in an oxalic acid aqueous solution of 0.05M adjusted to 16 占 폚 and subjected to anodic oxidation at 80 V for 5 seconds. Subsequently, the aluminum base was immersed in a 5 mass% aqueous phosphoric acid solution adjusted to 32 占 폚 for 20 minutes to enlarge the pore diameter of the oxide film. Thus, the anodic oxidation treatment and the hole diameter enlarging treatment were alternately repeated. The anodizing treatment and the hole diameter enlarging treatment were performed five times each. The obtained stamper was immersed in a 0.1 mass% aqueous solution of TDP-8 (manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, and then pulled up and dried overnight to perform mold release treatment.

The surface of the obtained porous alumina was observed by an electron microscope. As a result, a micro concavo-convex structure consisting of a substantially conical tapered concave portion having a distance of 180 nm and a depth of 150 nm between adjacent concave portions was formed.

[Example E1]

&Lt; Preparation of laminate >

The following materials were mixed to prepare an active energy ray curable composition.

22 parts by mass of ethylene oxide-modified dipentaerythritol hexaacrylate ("Kayadard DPEA-12", number of ethylene oxide structural units in one molecule n = 12, manufactured by Nippon Kayaku Co., Ltd.)

32 parts by mass ARONIX M-260 (trade name, manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13)

APG-700 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., average repeating unit of polypropylene glycol chain: 12) 32 parts by mass

9 parts by mass of BYK-3570 (trade name, a product of Big Chem Japan, diluted with silicone acrylate propylene oxide-modified neopentyl glycol diacrylate)

5 parts by mass of car lens MT PE1 (trade name, a compound having four SH groups, manufactured by Showa Denko K.K.)

1 part by mass Irgacure 184 (trade name, manufactured by Chiba Specialty Chemicals)

0.5 part (trade name, product name, manufactured by Chiba Specialty Chemicals)

0.1 part by mass of TDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd.)

A few drops of the active energy ray curable composition were dropped on the stamper and covered with a triacetyl cellulose film (FTTD80ULM (trade name), manufactured by Fuji Film) while spreading. Subsequently, the active energy rays-curable composition was photo-cured by irradiating ultraviolet rays at an energy of 1,000 mJ / cm ² at a film side. As shown in Fig. 1, a laminate having a fine concavo-convex structure with a distance w1 between adjacent convex portions of 180 nm and a convex portion height d1 of 150 nm was obtained.

<Evaluation>

The water contact angle, elastic modulus, antifouling property and protrusion unity of the obtained laminate were evaluated. Since the obtained laminate had a sufficiently low elastic modulus of 60 MPa and a water contact angle of 130 ° or more, it was possible to sufficiently remove the contamination due to dry adhesion, and it was also excellent in antifouling property without being projected. The results are shown in Table 7.

The abbreviations in Table 6 are as follows.

DPHA: dipentaerythritol hexaacrylate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

DPEA-12: ethylene oxide-modified dipentaerythritol hexaacrylate ("KAYARAD DPEA-12" manufactured by Nippon Kayaku Co., Ltd., n = 12 ethylene oxide structural units in one molecule)

DPHA-30EO: ethylene oxide-modified dipentaerythritol hexaacrylate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., the number of ethylene oxide structural units in one molecule n = 30)

M-260: Polyethylene glycol diacrylate ("Aronix M-260" manufactured by DOA Corporation, average repeating unit of polyethylene glycol chain: 13)

APG-700 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., average repeating unit of polypropylene glycol chain: 12)

C6DA: 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

BYK-3570: Silicone acrylate Propylene oxide-modified neopentyl glycol diacrylate Diluted product (manufactured by Big Chem Japan)

X-22-1602: Silicone acrylate (manufactured by Shin-Etsu Chemical Co., Ltd.)

PE1: car lens MT PE1 (trade name, a compound having four SH groups, manufactured by Showa Denko Co., Ltd.)

NR1: Car lens MT NR1 (trade name, a compound having three SH groups, manufactured by Showa Denko K.K.)

BD1: Car lens MT BD1 (trade name, a compound having two SH groups, manufactured by Showa Denko K.K.)

nOM: n-octylmercaptan (a compound having one SH group, manufactured by Elfatom Chem Japan)

IRG 184: Hydroxycyclohexyl phenyl ketone (&quot; Irgacure 184 &quot;, manufactured by Chiba Specialty Chemicals)

IRG 819: phenyl bis (2,4,6-trimethylbenzoyl) -phosphine oxide ("Ilgacure 819", manufactured by Chiba Specialty Chemicals)

TDP-2: polyoxyethylene alkylether phosphoric acid (trade name, manufactured by Nikko Chemicals Co., Ltd.)

On the other hand, in Tables 6 and 7, Examples 1 to 13 and Comparative Example 1 show Examples E1 to E13 and Comparative Example E1, respectively.

[Examples E2 to E13, Comparative Example E1]

A laminate was obtained in the same manner as in Example E1 except that the composition shown in Table 6 was used. The results are shown in Table 7.

In the laminates obtained in Examples E2 to E13, antifouling properties capable of easily removing stains without using water or alcohol were exhibited.

Examples E2 to E11 exhibited good antifouling properties because the indentation elastic modulus was 500 MPa or less and the water contact angle was 130 DEG or more. In particular, Examples 1 to 6, 8 and 10 exhibited particularly good antifouling properties since the indentation elastic modulus was 100 MPa or less. In Examples E12 and E13, since the amount of the compound having an SH group was increased, the antifouling property was excellent even though the water contact angle was 130 DEG or less.

Since the laminate of the present embodiment can easily remove contamination while maintaining excellent optical performance, it can be used in various displays such as televisions, mobile phones, portable game machines, touch panels, showcases, exterior covers, It is extremely useful as an enemy.

10:
11: substrate
12: Surface layer
13:
14:

Claims (20)

A laminate comprising a surface layer having a surface on which a fine uneven structure is formed,
Wherein the surface layer has a modulus of elasticity of less than 250 MPa and a slope of the coefficient of friction of the surface layer is 1.8 x ^10-3 or less. The method according to claim 1,
Wherein the slope of the friction coefficient of the surface layer is not less than -2.0 x 10 &lt; ^{-3 &} gt ;. 3. The method according to claim 1 or 2,
Wherein the slope of the friction coefficient of the surface layer is not less than -1.8 x 10 ^{-3 and not} more than 1.0 x 10 ^-3 . 4. The method according to any one of claims 1 to 3,
Wherein the surface layer has a modulus of elasticity of less than 160 MPa. 5. The method according to any one of claims 1 to 4,
Wherein the surface layer has a modulus of elasticity of less than 100 MPa. 6. The method according to any one of claims 1 to 5,
Wherein the water contact angle of the surface layer is 25 DEG or less or 130 DEG or more. 7. The method according to any one of claims 1 to 6,
Wherein the surface layer comprises a layer comprising a cured product of the active energy ray-curable resin composition. 8. The method of claim 7,
Wherein the active energy ray-curable resin composition comprises 1 to 55 parts by mass of a trifunctional or higher polyfunctional (meth) acrylate (A) and 10 to 95 parts by mass of a bifunctional (meth) acrylate (B) And the total amount of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass). 9. The method of claim 8,
Wherein the content of the trifunctional or higher polyfunctional (meth) acrylate (A) is 5 to 40 parts by mass and the content of the bifunctional (meth) acrylate (B) is 20 to 80 parts by mass. 9. The method of claim 8,
Wherein the content of the trifunctional or higher polyfunctional (meth) acrylate (A) is 10 to 30 parts by mass and the content of the bifunctional (meth) acrylate (B) is 30 to 70 parts by mass. 9. The method of claim 8,
Wherein the active energy ray-curable resin composition further comprises 3 to 85 parts by mass of a silicone (meth) acrylate (provided that the sum of the polymerizable components in the active energy ray-curable resin composition is 100 parts by mass, A) and (B) each exclude (C)). 10. The method of claim 9,
Wherein the active energy ray curable resin composition further contains 7 to 70 parts by mass of a silicone (meth) acrylate (provided that the sum of the polymerizable components in the active energy ray curable resin composition is 100 parts by mass, A) and (B) each exclude (C)). 8. The method of claim 7,
Wherein the active energy ray-curable resin composition comprises a compound (D) having an SH group. 14. The method of claim 13,
The active energy ray-curable resin composition preferably contains 0 to 95 parts by mass of a bifunctional or higher polyfunctional (meth) acrylate (E), 0 to 75 parts by mass of silicone (meth) acrylate, (D) is contained in an amount of 1 to 60 parts by mass (provided that the total of the polymerizable components is 100 parts by mass). 15. The method according to any one of claims 7 to 14,
Wherein the surface layer is composed of a layer comprising a cured product of the active energy ray-curable resin composition. 15. The method according to any one of claims 7 to 14,
Wherein the surface layer is composed of a layer comprising a cured product of the active energy ray-curable resin composition and a surface treatment layer as a topmost layer formed on the layer of the cured product of the active energy ray-curable resin composition. 16. The method according to any one of claims 1 to 15,
And the pitch of the fine uneven structure is 100 nm or more and 250 nm or less. An antireflective article comprising the laminate according to any one of claims 1 to 17. An image display apparatus comprising the laminate according to any one of claims 1 to 17. A touch panel comprising the laminate according to any one of claims 1 to 17.

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